CN100337916C

CN100337916C - Hydrotalcite compound process for producing the same, and agricirultural film containing the same

Info

Publication number: CN100337916C
Application number: CNB998025739A
Authority: CN
Inventors: 高桥秀夫; 冈田彰
Original assignee: Kyowa Chemical Industry Co Ltd
Current assignee: Kyowa Chemical Industry Co Ltd
Priority date: 1998-12-01
Filing date: 1999-11-29
Publication date: 2007-09-19
Anticipated expiration: 2019-11-29
Also published as: ATE471298T1; JP2001002408A; SK11502000A3; EP1052223B1; AU1411300A; KR20010034281A; HUP0100823A2; DE69942502D1; CN1289307A; CA2319441A1; TR200002346T1; EP1052223A1; KR100985427B1; HUP0100823A3; WO2000032515A1; JP4054144B2; US6418661B1; PL342134A1; EP1052223A4

Abstract

A hydrotalcite compound which has the excellent ability to absorb infrared rays and has excellent light transmission when contained in an agricultural film; a process for producing the compound; and an infrared absorber and an agricultural film both containing the compound. The hydrotalcite compound is characterized by retaining as the interlayer anions at least one kind of anions selected among ions of silicon-, phosphorus-, and boron-containing polymeric oxyacids and another kind of anions.

Description

Hydrotalcite-based compound and its method for making and the agricultural film that contains this compound

Technical field

The present invention relates to have excellent infrared ray absorption ability and be contained in occasion in the agricultural film show excellent light by characteristic hydrotalcite-based compound and method for making, with this hydrotalcite-based compound as the infrared absorbent of effective constituent and the agricultural film that contains this infrared absorbent.

Background technology

Always, in the greenhouse productions of farm crop and the cultivation of a heatable brick bed road, be extensive use of agricultural film, wished that this agricultural film has light trafficability characteristic and heat retaining property concurrently.That is to say, greenhouse that is subjected to the solar ray of wavelength 0.29 μ m～4.3 μ m daytime and heats up or the temperature in a heatable brick bed road sharply become low temperature at particularly fine night at night because of irradiation cools off, and the rapid cooling in these greenhouses or a heatable brick bed road produces ill effect to the growth of farm crop.Sharply though low temperatureization has various major reasons, has a kind of saying to be, because the thermal radiation (with long wavelength's infrared radiation) to the outside is one of essential factor of low temperatureization from ground and cultivated plant at night.In this saying, having taked can E λ d λ (erg/scm from the blackbody radiation of planck formula (following formula (3)) ²) calculate thermal-radiating method:

Eλ·dλ＝2πhC^2/[λ^5{e^(hC/λkT)-1}]·dλ ……(3)

Wherein, λ: wavelength; H: quantum of action; C: the very aerial light velocity; K: Boltzmann constant; T: absolute temperature

Calculate thus and point out, emit infrared particularly with 1000cm 30～-10 ℃ temperature range ^-1400～2000cm for maximum ^-1Infrared rays (blackbody radiation energy).

Therefore has the heat retaining property film that absorbs infrared capable for preventing the rapid low temperatureization in such greenhouse or a heatable brick bed road, having used.Such heat retaining property film, or adopting the thermoplastic resin itself as base material is to have the material that absorbs infrared capable, or adopting to contain in the thermoplastic resin has the absorption infrared capable and (particularly absorbs 400～2000cm ^-1Ultrared ability) material, i.e. infrared absorbent makes film have the ultrared ability of absorption with this method.As infrared absorbent, for example can use oxyhydroxide or oxide compound, aluminate, borate or vitriol, the hydrotalcite-based compound etc. of silicon-dioxide and silicate, lithium, calcium, magnesium, aluminium etc.

Wherein, hydrotalcite-based compound, so, now proposed a plurality of patent applications because of its infrared ray absorption ability and more excellent more particularly useful than the oxyhydroxide of silicon-dioxide and silicate or lithium, calcium, magnesium, aluminium etc. or oxide compound or aluminate, borate or vitriol etc. as infrared absorbent in the trafficability characteristic of the light of the occasion that cooperates with resin.(hydrotalcite-based compound is the complex hydroxide salt with interlayer multiple laminate structure that the complex hydroxide layer that formed by magnesium and aluminium (basic layer) and negatively charged ion (for example carbanion) and middle water constituted.Formula in this patent (1) and formula (4) are represented is to have the basic layer that is made of magnesium and aluminium or magnesium and other divalent metal and aluminium and the complex hydroxide salt of the interlayer that negatively charged ion and middle water constituted, formula (2) and (5) are represented be composition of its basic layer different, have by lithium and aluminium or lithium and basic layer and the complex hydroxide salt of the interlayer that negatively charged ion and middle water constituted that divalent metal and aluminium constitute, be to have equally or the compound of similar structures with above-mentioned hydrotalcite-based compound.Thus, in this patent, these all are referred to as and are expressed as hydrotalcite-based compound, and the hydrotalcite-based compound with formula (1) and (4) expression is called magnesium-aluminum hydrotalcite compounds, the hydrotalcite-based compound of representing with formula (2) and (5) is called lithium-aluminum hydrotalcite compounds).

The patent of relevant magnesium-aluminum hydrotalcite compounds of enumerating has, for example, (=USP 4 for special public clear 62-31744,686,791 and EP 142,773), special public clear 62-53543, special public clear 62-41247, special public clear 63-175072, special public clear 63-115743, special public clear 63-149147, special public clear 63-149148, special public clear 64-6041, special fair 4-11107, special fair 6-6363, special fair 6-6364 and the flat 9-176390 of Te Kai etc.; What the patent of relevant lithium-aluminum hydrotalcite compounds was enumerated has, for example, (=EP 672 for Te Kaiping 7-300313,619), the spy opens flat 9-142835 (=EP 790,214), the spy open the flat again 9-800828 of flat 9-279124, spy (=USP 5,767,179 and EP 778,241), the spy opens that flat 9-235420 (=EP 781,800), spy open flat 10-52895, the spy opens flat 10-235776 and the flat 10-226739 of Te Kai etc.

Though represented hydrotalcite-based compound has composition formula miscellaneous in these applications, represents with following formula (4) or (5) substantially.

The general formula of＜magnesium-aluminum hydrotalcite compounds 〉

[{Mg _y1M ²⁺ _y2} _1-XAl _X(OH) ₂] ^X+[A ^n- _X/n·bH ₂O] ^X- …(4)

(basic layer) (interlayer)

In above-mentioned formula,

M ²⁺At least a divalent metal ion in expression zinc, calcium and the nickel.

A ^N-Expression n valency negatively charged ion, for example, that enumerates has a Cl ^-, Br ^-, I ^-, NO ₃ ^-, ClO ₄ ^-, H ₂PO ₄ ^-, HBO ₃ ^2-, SO ₄ ^2-, CO ₃ ^2-, SiO ₃ ^2-, HPO ₄ ^2-, PO ₄ ^3-, Fe (CN) ₆ ^3-, Fe (CN) ₄ ^4-Deng mineral acid and organic acid.

X, y1, y2 and b represent to satisfy the positive number of following condition separately.

0＜X≤0.5、y1+y2＝1、y1≤1、y2＜1、0≤b＜2

The general formula of＜lithium-aluminum hydrotalcite compounds 〉

[(Li _1-XG ²⁺ _X)Al ₂(OH) ₆] ^(1+X)+[(A ^n-) _(1+X)/n·bH ₂O] ^(1+X)-…(5)

(basic layer) (interlayer)

G ²⁺At least a divalent metal ion in expression magnesium, zinc, calcium and the nickel.A ^N-Expression n valency negatively charged ion,

X and b represent to satisfy the positive number of following condition separately.

0≤X＜1、0≤b＜5

Most occasions therein use interlayer to keep the hydrotalcite-based compound (following table is shown carbanion type hydrotalcite-based compound) of carbanion.

But, in for example occasion of carbanion type magnesium-aluminum hydrotalcite compounds, to 400～800 and 1400cm ^-1Though near infrared ray absorption ability is good, to being positioned at 900～1300cm ^-1Near infrared rays lacks receptivity.It is contained in only in 700 and 1300～1500cm as infrared absorbent ^-1Near the infrared ray absorption ability is arranged polyethylene as the occasion in the agricultural film of base material, the infrared ray absorption ability of this agricultural film is the adduction of the infrared ray absorption ability of polyethylene and infrared absorbent, but still lacks 900～1300cm ^-1Near ultrared receptivity promptly is the low material of heat retaining property.Also have, carbanion type lithium-aluminum hydrotalcite compounds is at 1000cm ^-1Near have and absorb but absorb not by force, and from the infrared ray absorption ability of integral body, it and carbanion type magnesium-aluminum hydrotalcite compounds are equal extent.Also have, compare, show excellent light trafficability characteristic, also do not have the material that fully to be satisfied with though contain the agricultural film of these (hydrotalcite-based compounds) with the material that contains other infrared absorbents.

As the method for the infrared ray absorption ability that improves magnesium-aluminum hydrotalcite compounds, there is in the public clear 62-31744 of spy (=USP 4,686,791 and EP 142,773) institute illustrative by with H ₂PO ₄ ^-, HPO ₄ ^2-, PO ₄ ^3-, HBO ₃ ^2-With SiO ₃ ^2-Deng so-called silicon class, Phosphorus and boron class monomer oxygen acid radical ion remain on interlayer so that at 900～1300cm ^-1Neighbouring can have the infrared ray absorption ability, also has, even also existing same consideration in lithium-aluminum hydrotalcite compounds.But, be contained in occasion in the agricultural film maintaining these anionic hydrotalcite-based compounds as infrared absorbent, though the heat retaining property of agricultural film is improved to some extent, but not the material that can fully satisfy, in addition, the occasion of the light trafficability characteristic of film and carbanion type hydrotalcite-based compound always is equal or poorer.

Also have, recently, for further improving the infrared ray absorption ability of hydrotalcite-based compound, (=EP 708 for Te Kaiping 8-21791,056) (=USP 5 with the flat again 9-800828 of spy, 767,179 and EP 778,241) once proposed to maintain with the silicate ion of condensation and/or the phosphate anion of condensation (hereinafter referred to as silicon class and/or Phosphorus poly oxygen acid radical ion) hydrotalcite-based compound as interlayer anion.These to be silicon class and Phosphorus oxygen acid radical ions by maintaining multimerization at interlayer make its thereby to improve the infrared ray absorption ability than silicon class and Phosphorus oxygen acid radical ion more of keeping be purpose more.And then, can make the specific refractory power of thermoplastic resin used in the specific refractory power of hydrotalcite-based compound and the agricultural film more approaching by same method, therefore, its light trafficability characteristic of film that contains these also can improve.Specifically, its interlayer at (003) face or (002) face of carbanion type hydrotalcite-based compound is spaced apart about 7.6 , specific refractory power is 1.51～1.53, as open flat 8-217912 (=EP708 the spy, 056) (=USP 5 with the flat again 9-800828 of spy, 767,179 and EP778,241) shown in like that, the interval of interlayer of hydrotalcite-based compound that for example maintains silicon class poly oxygen acid radical ion at (003) face or (002) face for maximum, 11.9  have been expanded as, specific refractory power is reduced to 1.49～1.52 thus, also have, the thermoplastic resin of in agricultural film, using, for example the specific refractory power with ethylene-vinyl acetate copolymer is 1.49～1.50, open flat 8-217912 (=EP708 containing useful spy, 056) with the flat again 9-800828 of spy (=USP 5,767,179 and EP778,241) like that hydrotalcite-based compound is contained in occasion in the agricultural film shown in, the light trafficability characteristic of film improves.

But, though these result of trackings such as the inventor is the infrared ray absorption ability that can improve in the agricultural film, light trafficability characteristic aspect more then is equal or poorer with always hydrotalcite-based compound.Though the light trafficability characteristic of film does not have the reason of raising also indeterminate, but can think that (=EP 708 opening flat 8-217912 the spy, 056) with flat again the 9-800828 (=USP5 of spy, 767,179 and EP 778,241) described in the processing temperature of the hydrotalcite-based compound that maintains silicon class and Phosphorus poly oxygen acid radical ion when mixing in the used resin of agricultural film be one of cause.

In view of the above, up to now, in the well-known infrared absorbent, also not having a kind of is can fully satisfy excellent infrared ray absorption ability can also can give excellent this two aspect characteristic of light trafficability characteristic in the occasion that it is contained in the agricultural film again.

Disclosure of an invention

The objective of the invention is to, provide when having excellent infrared ray absorption ability, again the material that is contained in the light trafficability characteristic that can give the film excellence under the agricultural film occasion and method for making thereof and with this material as the infrared absorbent of effective constituent with contain agricultural film this infrared absorbent, that have excellent heat retaining property and excellent light trafficability characteristic concurrently.

Present inventors etc. are considering above-mentioned problem and found that of studying: interlayer maintain be at least a negatively charged ion in silicon class, the Phosphorus and boron class oxygen acid radical ion and its partly or entirely be at least a negatively charged ion in silicon class, the Phosphorus and boron class poly oxygen acid radical ion and other anionic, with the hydrotalcite-based compound of following formula (1) or (2) expression, has excellent infrared ray absorption ability, and the occasion that contains it in agricultural film can be given the light trafficability characteristic of film excellence, so finished the present invention.In view of the above, this hydrotalcite-based compound is contained in occasion in the agricultural film as infrared absorbent, can obtaining having concurrently the film of excellent heat retaining property and excellent light trafficability characteristic.

＜magnesium-aluminum hydrotalcite compounds 〉

[{Mgy1M2+y2}1-xAlx(OH)2]x+[(A)z1(B)z2·bH2O]x- ……(1)

(basic layer) (interlayer)

M ²⁺At least a divalent metal ion in expression zinc, calcium and the nickel.A represents to be at least a negatively charged ion in silicon class, the Phosphorus and boron class oxygen acid radical ion and its part and/or all to be at least a negatively charged ion in silicon class, the Phosphorus and boron class poly oxygen acid radical ion, B represents it is at least a negatively charged ion in the negatively charged ion beyond the A

X, y1, y2, z1, z2 and b satisfy following condition separately:

X is 0＜X≤0.5; Y1 and y2 are y1+y2=1,0＜y1≤1,0≤y2＜1; Z1 and z2 are 0＜z1,0＜z2; B is 0≤b＜2.

＜lithium-aluminum hydrotalcite compounds 〉

[(Li _y1G ²⁺ _y2)Al ₂(OH) ₆] ^X+[(A) _Z1(B) _Z2·bH ₂O] ^X-…(2)

(basic layer) (interlayer)

G ²⁺At least a divalent metal ion in expression magnesium, zinc, calcium and the nickel.A is expressed as at least a negatively charged ion in silicon class, the Phosphorus and boron class oxygen acid radical ion and its part and/or all is at least a negatively charged ion in silicon class, the Phosphorus and boron class poly oxygen acid radical ion,

B is expressed as at least a negatively charged ion in the A negatively charged ion in addition,

Y1, y2, X, z1, z2 and b satisfy following condition separately:

Y1 and y2 are 0＜y1≤1,0≤y2＜1,0.5≤(y1+y2)≤1;

X is X=y1+2y2;

Z1 and z2 are 0＜z1,0＜z2;

B is 0≤b＜5.

That is to say, hydrotalcite-based compound of the present invention is that to maintain at interlayer be the silicon class, at least a negatively charged ion in the Phosphorus and boron class oxygen acid radical ion, and it partly or entirely is the silicon class, the material of at least a anionic A (following table is shown as the A negatively charged ion) in the Phosphorus and boron class poly oxygen acid radical ion and this negatively charged ion B (following table is shown as the B negatively charged ion) in addition, and it still has well-known so far various ionic hydrotalcite-based compound concurrently, (=EP 708 for Te Kaiping 8-217912,056) (=USP 5 with the flat again 9-800828 of spy, 767,179 and EP778,241) hydrotalcite-based compound that maintains silicon class and Phosphorus poly oxygen acid radical ion described in, perhaps these merging are made the infrared ray absorption ability of the excellence that the occasion that is used as infrared absorbent all do not obtain and just can give the material of characteristic of the light trafficability characteristic of film excellence the occasion that it is contained in agricultural film.

Though reason is also not really clear, but, (=EP 708 for Te Kaiping 8-217912,056) with the flat again 9-800828 of spy (=USP 5,767,179 and EP 778,241) hydrotalcite-based compound of having put down in writing in that maintains silicon class and Phosphorus poly oxygen acid radical ion that contains many middle waters, as previously mentioned, enlarged interlayer, and made its specific refractory power also approaching with thermoplastic resin with agricultural film.But, because the expansion of interlayer, according to differential thermal analysis (DTA), middle water is just breaking away from below 150 ℃.On the other hand, infrared absorbent is contained in agricultural film with the occasion in the thermoplastic resin, normally under 140～200 ℃ processing temperature, mixes and contain.Infer thus, occasion in aforementioned hydrotalcite-based compound is contained in agricultural film usefulness thermoplastic resin as infrared absorbent, 140～200 ℃ processing temperature breaks away from the middle water in this infrared absorbent, the interlayer that has enlarged narrows down again again, specific refractory power also has big variation, just becomes the material of light trafficability characteristic difference in the occasion of final filming.This phenomenon also can be from mixing into agricultural film to beginning with the thermoplastic resin and its light trafficability characteristic of the occasion of filming descends more that this can imagine out with regard to this infrared absorbent of having removed middle water.Also have, can envision, this infrared absorbent has maintained a plurality of silicon classes or Phosphorus poly oxygen acid radical ion, when taking off middle water during by these compounds synthetic or by thermal treatment, generated silicate and phosphate compounds partly in crystallization inside (interlayer portion), this just produces ill effect to the light trafficability characteristic of film.

Know that maintain different therewith A negatively charged ion negatively charged ion in addition, for example the middle water of the hydrotalcite-based compound of sulfate ion, carbanion, chlorion or nitrate ion etc. breaks away from about 200～240 ℃.Hydrotalcite-based compound of the present invention is to maintain A negatively charged ion and the anionic material of B, for example, maintaining with sulfate ion, carbanion, chlorion or nitrate ion etc. are as the anionic occasion of B, their character has been added at interlayer and has maintained on their hydrotalcite-based compound, make the middle water that under 140～200 ℃ processing temperature, still keeps a part to be difficult to break away from, relaxed its interlayer ratio that narrows at interval, variations in refractive index is diminished, therefore thing of the present invention is being fitted into the occasion of agricultural film as infrared absorbent, can infer that it makes the decline of the light trafficability characteristic difficulty that becomes.Also have, hydrotalcite-based compound of the present invention evenly remains on interlayer because of each negatively charged ion, so infer that the generation of silicate compound and phosphate compounds is also few.

The interlayer anion of hydrotalcite-based compound of the present invention: B is the negatively charged ion beyond the A, be that it is silicon class, Phosphorus and boron class oxygen acid radical ion at least a negatively charged ion in addition, serve as preferred wherein with at least a in sulfate ion, carbanion, chlorion and the nitrate ion, with at least a negatively charged ion in sulfate ion and the carbanion for more preferably.

When for example being contained in thing of the present invention in the resin, from dispersed viewpoint, average aggregate particle size below 5 μ m and BET[Brunner-Emmett-Teller] specific surface area is at 30m ²/ g is following to be preferred.Also have, for obtaining better dispersiveness, product of the present invention also can use at least a surface treatment agent in the fatty acid ester that is selected from higher fatty acid, anionic species tensio-active agent, phosphoric acid ester, nonionic surface active agent, silane, titanic acid ester and aluminium class coupler and polyvalent alcohol to carry out surface treatment.Also have, be the problem of avoiding foaming with flake, it is also passable that hydrotalcite-based compound of the present invention or its surface-treated material are partly or entirely removed its middle water with thermal treatment.

Because hydrotalcite-based compound of the present invention has excellent infrared ray absorption ability and give the characteristic of the light trafficability characteristic of film excellence in being contained in agricultural film the time, therefore is very suitable for the infrared absorbent as agricultural film.Especially, as infrared absorbent, in its formula (1) and (2) with 0.1≤[(B) _Z2Total valence mumber]/scope of X≤0.8 is preferred.In view of the above, containing in film with respect to the used thermoplastic resin of agricultural film, is the agricultural film that hydrotalcite-based compound of the present invention constituted of 1～30 weight %, and has excellent infrared ray absorption ability and excellent light trafficability characteristic concurrently.

Hydrotalcite-based compound of the present invention, can be at least a negatively charged ion beyond the A negatively charged ion by beginning to make interlayer anion, the hydrotalcite-based compound of sulfate ion, carbanion, chlorion, nitrate ion and organic acid ion etc. and then for example by preparing with the anionic ion-exchange of A., be preferred then wherein with the anionic ion-exchange of A with after making at least a anionic hydrotalcite-based compound that maintains in sulfate ion, carbanion, chlorion and the nitrate ion; More to make the hydrotalcite-based compound of maintenance based on sulfate ion when reaction is synthetic, the method for carrying out ion-exchange with the A negatively charged ion is put preferred especially because of preparation and the auxiliary infrared ray absorption ability that will speak of in the back in addition etc. that it can be easy and cheap thereafter.

The simple declaration of accompanying drawing

The infrared rays (IR) that Fig. 1 shows the thick film of the 100 μ m of hydrotalcite-based compound of the present invention (powder) of the embodiment 2 that contains 10 weight % in metallocene PE (PE) absorbs spectrogram.

The infrared rays (IR) that Fig. 2 shows the thick film of the 100 μ m of hydrotalcite-based compound of the present invention (powder) of the embodiment 3 that contains 10 weight % in metallocene PE (PE) absorbs spectrogram.

The infrared rays (IR) that Fig. 3 shows the thick film of the 100 μ m of hydrotalcite-based compound of the present invention (powder) of the embodiment 9 that contains 10 weight % in metallocene PE (PE) absorbs spectrogram.

The infrared rays (IR) that Fig. 4 shows the thick film of the 100 μ m of hydrotalcite-based compound (powder) of the comparative example 1 that contains 10 weight % in metallocene PE (PE) absorbs spectrogram.

Fig. 5 shows just, and the infrared rays (IR) of 100 μ m thick film of metallocene PE (PE) absorbs spectrogram.

The preferred plan that carries out an invention

Hydrotalcite-based compound of the present invention can resemble and prepare following.Preparation method as magnesium-aluminum hydrotalcite compounds has, and (=USP 3,796 for special public clear 47-32198,792), special public clear 50-30039, special public clear 51-29129 and special fair 4-73457 (=USP 4,675,356 and EP 189, known method for making such as 899) is for example by Mg and M ²⁺Muriate or the muriate of nitric acid oxygen or sulfate liquor or oxyhydroxide and Al or nitrate or sulfate liquor or sodium aluminate solution and alkaline solution reaction, synthesized interlayer and maintained for example magnesium of sulfate ion, carbanion, chlorion or nitrate ion-aluminum hydrotalcite compounds slurry.The mol ratio of divalent metal and Al and Mg and M ²⁺Though mol ratio can modus ponens (1) shown in arbitrary value in the scope, for more preferably, 0.25≤X≤0.35 is for preferred especially as the preferred 0.2≤X of X≤0.5,0.2≤X≤0.4.Also have, owing to the M that is shown in the example ²⁺The atoms of elements amount all the nucleidic mass than magnesium is big, M ²⁺Mol ratio when becoming big, just make the molecule quantitative change of magnesium-aluminum hydrotalcite compounds big, finally the infrared ray absorption ability as infrared absorbent just descends, based on this fact, little with its (mol ratio) serves as preferred.Therefore, y2≤0.5 is preferred, and y2≤0.3 is for more preferably.Secondly, such synthetic magnesium-aluminum hydrotalcite compounds slurry in aqueous medium, is become average aggregate particle size and the adjusted magnesium of BET specific surface area-aluminum hydrotalcite compounds slurry by the hydrothermal treatment consists under for example about 120 ℃～about 250 ℃ temperature and the time conditions of about 1～about 40h.

Preparation method as lithium-aluminum hydrotalcite compounds has, Te Kaiping 9-142835 (=EP790,214) and the spy open known method for makings such as flat 9-279124, the aluminum water solution by for example sodium aluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate etc. or the lithium aqueous solution of aluminium hydroxide, carbonate aluminum,basic and Lithium Sulphate, lithium chloride, lithium nitrate, lithium hydroxide or Quilonum Retard etc., also have as M ²⁺For example the magnesium aqueous solution of sal epsom, magnesium chloride, magnesium nitrate etc. or magnesiumcarbonate, magnesium hydroxide etc. and alkaline solution react, and synthetic interlayer maintains for example lithium of sulfate ion, carbanion, chlorion or nitrate ion-aluminum hydrotalcite compounds slurry.Li and/or G ²⁺Mol ratio and Al and Li and G ²⁺Though mol ratio can modus ponens (2) shown in arbitrary value in the scope, be 0.7≤(y1+y2)≤1 serve as preferably with y1+y2,0.9≤(y1+y2)≤1 for more preferably, 0.95≤(y1+y2)≤1 for preferred especially.To Li and G ²⁺Mol ratio, because of G ²⁺Mol ratio be difficult to keep with regard to the structure that makes lithium-aluminum hydrotalcite compounds when becoming big, little with its (mol ratio) serves as preferred.Therefore, y2≤0.5 is preferred, and y2≤0.2 is for more preferably, and y2≤0.1 is for preferred especially.Secondly, such synthetic lithium-aluminum hydrotalcite compounds slurry in aqueous medium, by the hydrothermal treatment consists under for example about 80 ℃～about 250 ℃ temperature and the time conditions of about 1～about 40h, become the adjusted lithium of average aggregate particle size and BET specific surface area-aluminum hydrotalcite compounds slurry.

Then, by above-mentioned magnesium-aluminium or lithium-aluminum hydrotalcite compounds slurry (except the carbanion type) are mixed with siliceous class, solution Phosphorus and boron class oxygen acid radical ion, make negatively charged ion when synthetic and silicon class, Phosphorus and boron class oxygen acid radical ion carry out ion-exchange, just can prepare as interlayer anion and maintain at least a anionic in for example the A negatively charged ion and sulfate ion, carbanion, chlorion and nitrate ion and adjusted the hydrotalcite-based compound of average 2 particle diameters and BET specific surface area.

Occasion from carrying out ion-exchange in addition with aforesaid method synthetic carbanion type magnesium-aluminium or lithium-aluminum hydrotalcite compounds slurry and A negatively charged ion, can adopt and begin to use sulfuric acid, hydrochloric acid, the acid solution of nitric acid or acetic acid and so on low molecular weight organic acid etc., the part of interlayer and/or whole carbanion and sulfate ion, chlorion, nitrate ion or organic acid ion carry out after the ion-exchange, use for example water glass again, the such alkaline matter of sodium phosphate or Sodium Tetraborate carries out ion-exchange and prepares, and also can partly carry out ion-exchange with the such directly sour and carbanion of phosphoric acid and prepare.

In above-mentioned each method for making, before the anionic ion-exchange of A, add the surface treatment agent say later and carry out surface treatment, and then carry out ion-exchange with the A negatively charged ion and also be fine.

Though hydrotalcite-based compound of the present invention not only can but also can prepare with other method for making with the above-mentioned method for making of enumerating, and its raw material and manufacturing cost are uprised.Also have, the method with acid in above-mentioned method for making sustains damage the crystallization of hydrotalcite-based compound, probably can harm its dispersiveness.More when making preparation, carbonic anhydride also has problems owing to producing.Thus, making when being synthesized by reaction with the carbanion type serves as preferred, wherein preferred with the hydrotalcite-based compound that mainly maintains sulfate ion between prepared layer with the epigenesist, and it has auxiliary infrared ray absorption ability in addition easily and cheaply because of its preparation.

As for the anionic ion-exchange condition of A, drop into the solution of siliceous class, Phosphorus and boron class oxygen acid radical ion when usually the hydrotalcite-based compound slurry being stirred, keep 1min～24h then at normal temperatures and just can carry out ion-exchange, but so that to keep 1～24h serve as preferred (also can heating before silicon class, Phosphorus and boron class oxygen acid radical ion input) more than 60 ℃, keep 1～24h more than 70 ℃ for more preferably, keep 1～24h more than 80 ℃ for preferred especially.Otherwise, will use pressurized vessel more than 100 ℃, also bad from the productivity viewpoint more than 24h.

The oxygen acid radical ion of enumerating as the A negatively charged ion of hydrotalcite-based compound of the present invention that silicon class, Phosphorus and boron class are arranged, for example, as the silicon class with SiO ₃ ^2-, Si ₂O ₅ ^2-, Si ₃O ₇ ^2-, Si ₄O ₉ ^2-, (HSiO ₃) ^-, (HSi ₂O ₅) ^-Deng (Si _nO _2n+1) ^2-Or (HSinO _2n+1) ^-The ion of expressions such as (n are the integer more than 1); As Phosphorus with PO ₄ ^3-, (HPO ₄) ^2-, (H ₂PO ₄) ^-, (P ₂O ₇) ^4-, (P ₃O ₁₀) ^5-Or (P ₃O ₉) ^3-, (P ₄O ₁₂) ^4-, (P ₆O ₁₈) ^6-Deng (P _nO _3n) ^N-Or [(PO ₃) _n] ^N-The ion and the (H of expressions such as (n are the integer more than 3) ₂P ₂O ₇) ^2-The product of the some additions of H base of such Phosphorus oxygen acid radical ion etc.; BO as the boron class ₃ ^3-, (HBO ₃) ^2-, (H ₂BO ₃) ^-, [B ₃O ₃(OH) ₄] ^-, [B ₅O ₆(OH) ₄] ^-Or [B ₄O ₅(OH) ₄] ^2-Deng monomer oxygen acid radical ion and poly oxygen acid radical ion, but because hydrotalcite-based compound of the present invention improves the light trafficability characteristic when improving the infrared ray absorption ability and being contained in the agricultural film is purpose, thus it be keep a part with/all be at least a anionic material in silicon class, the Phosphorus or boron class poly oxygen acid radical ion.

These silicon classes of specifically enumerating, raw material Phosphorus or boron class oxygen acid radical ion have, the water glass of silicon class, 1,2, No. 3 water glass and unbodied SiO ₂Be dissolved in the material of the such alkali hydroxide metal water solution of NaOH etc.; The Phosphorus phosphoric acid and the phosphoric acid alkali metal aqueous solution (also comprise and contain H base person); With the boric acid of boron class, Sodium Tetraborate, sodium tetraborate etc.

B is at least a negatively charged ion in the A negatively charged ion in addition, that can enumerate has, chlorion for example, bromide anion, iodide ion, nitrate ion, carbanion, sulfate ion, cross chloranion, inorganic acid radical ion and formate ions such as iron cyanide ion, acetate ion, organic acid ions such as oxalate denominationby, but wherein with sulfate ion, carbanion, at least a negatively charged ion in chlorion and the nitrate ion is preferred, with at least a negatively charged ion in sulfate ion and the carbanion for more preferably, because sulfate ion wherein has the 1100cm of being absorbed in ^-1Near the infrared ray absorption ability, even part is when keeping, this puts and considers from improving the infrared ray absorption ability, also is particularly preferred.

In the occasion of using hydrotalcite-based compound of the present invention as infrared absorbent, silicon class, the many persons of maintenance dose Phosphorus or boron class oxygen acid radical ion are preferred, but will make the infrared ray absorption ability drop of the basic layer that comes from original hydrotalcite-based compound too much, be matched with the occasion of agricultural film, consequently the light trafficability characteristic descends.Also have, just lack the ultrared ability that absorbs when very few, make the heat retaining property of agricultural film become not high thus, (total valence mumber: 20～90% X-) serve as preferably to the theoretical amount of the interlayer anion that calculates with the basic layer that accounts for from formula (1) or (2), accounts for 30～80% for more preferably.

Though in the preceding paragraph literal, shown the maintenance dose of preferred silicon class, Phosphorus or boron class oxygen acid radical ion, but in the reality, know, Phosphorus or boron class oxygen acid radical ion has form miscellaneous, so for keeping in the hydrotalcite-based compound of these (negatively charged ion) in part, silicon class, oxygen acid radical ion Phosphorus or the boron class are to be difficult to judge which type of form to remain in interlayer with, so it is difficult limiting the valency of oxygen acid radical ion, judge that how much what account for the total valence mumber of interlayer anion is difficulty very.For this reason, inquired into the method for judging with method for distinguishing, found that, be expressed as with the ratio of interlayer as the anionic valence mumber beyond the A of B negatively charged ion existence.In other words when adopting this method, it is preferred that the total number of the anionic valence mumber of B accounts for 10～80% of the total valence mumber of interlayer anion.That is, 0.1≤((B) _Z2Total valence mumber)/X≤0.8 is preferred.Also have, 20～70% for more preferably, thus, and 0.2≤((B) _Z2Total valence mumber)/X≤0.7 is for more preferably.In addition, what A was represented is anionic silicon class and/or the Phosphorus oxygen acid radical ion mole number (Q) by Si and/or P, with and Al ₂O ₃The ratio of mole number when representing, the occasion of formula (1), preferred 0＜Q/ is (as Al ₂O ₃Mole number)≤6, more preferably 0＜Q/ is (as Al ₂O ₃Mole number)≤4, most preferably 0＜Q/ is (as Al ₂O ₃Mole number)＜2.The occasion of formula (2), by the mole number (R) of Si, preferred 0＜R/ is (as Al ₂O ₃Mole number)≤3, more preferably 0＜R/ is (as Al ₂O ₃Mole number)≤2, most preferably 0＜R/ is (as Al ₂O ₃Mole number)＜1.

Hydrotalcite-based compound of the present invention can partly or wholly be removed middle water by with its powder thermal treatment 1～20h under 150～250 ℃ of temperature.

As the method for the hydrotalcite-based compound of interlayer anion and hydrotalcite-based compound always powder x-ray diffraction (XRD) method and compositional analysis method, infrared ray absorption assay method are arranged as difference A negatively charged ion and the B negatively charged ion of having kept of the present invention.

Just can confirm to have remained in the silicon class of interlayer, the existence of Phosphorus and boron class poly oxygen acid radical ion by the interplanar distance of the generation of measuring the diffractogram research hydrotalcite-based compound obtain with xrd method and interlayer.For example, the interlayer of carbanion that is obtained by xrd method and chlorion, silicon class monomer oxygen acid radical ion type hydrotalcite-based compound is 7.4～7.8  at (003) face or (002) face at interval, is 8.2～8.8  at (003) face or (002) face of sulfate ion and nitrate ion, Phosphorus monomer oxygen acid radical ion type hydrotalcite-based compound.In these hydrotalcite-based compounds, for example the silicon class, when poly oxygen acid radical ion Phosphorus and the boron class carries out ion-exchange, the interval of its (003) face or (002) face nearly all becomes more than 9 .Just can predict thus at interlayer and whether contain and how to contain poly oxygen acid radical ion.But, in silicon class, Phosphorus and occasion that boron class poly oxygen acid radical ion maintenance dose is few and the occasion of having removed middle water by thermal treatment, the situation that misfits above-mentioned saying is arranged.

In the compositional analysis method, the mol ratio of basic layer and anionic total valence mumber of interlayer are obtained in the analysis that is the metallic cation by basic layer, also have, obtain the anionic total valence mumber of B from the anionic analysis of B, by they difference and the analysis of silicon, phosphorus and boron just can predict silicon class, Phosphorus and boron class the oxygen acid radical ion in whether and how contain poly oxygen acid radical ion.

Si-O-Si and P-O-P key in the silicon class in the interlayer, Phosphorus poly oxygen acid radical ion are the occasion of linearity, can be at 1250～1350cm with the infrared absorption spectrometry method ^-1Detect near the absorption spectrum.

Comprehensive these analytical resultss of judgement just can come hydrotalcite-based compound of the present invention and hydrotalcite-based compound difference always.

Hydrotalcite-based compound of the present invention is matched with occasion in the resin, though can intactly directly cooperate, its dispersiveness also is good, but better for making with the intermiscibility of resin, processibility etc., can do the surface with at least a surface treatment agent in the fatty acid that is selected from higher fatty acid class, anionic species tensio-active agent, phosphoric acid ester, silane, titanic acid ester and aluminium class coupler and polyvalent alcohol and handle.

Specifically the tensio-active agent of the preferred use that can enumerate has: stearic acid; oleic acid; erucic acid; palmitinic acid; the an alkali metal salt of senior fatty acid such as lauric acid and these higher fatty acid; stearyl alcohol; the sulfuric acid of higher alcoholss such as oleyl alcohol; the sulfuric acid of polyglycol ether; acyl ammino sulfuric acid; ether closes sulfonate; ester closes sulphonate; acyl ammino alkylallyl sulfonate; ether closes anionic species tensio-active agents such as alkylallyl sulfonate; former phosphoric acid and oleyl alcohol; the list of stearyl alcohol etc. or dibasic acid esters or both mixtures; the phosphoric acid ester of these acidity or an alkali metal salt or amine salt etc.; the vinyl Ethoxysilane; γ-methacryloxypropyl trimethoxy silane; vinyl-three (2-methoxyl group-oxyethyl group) silane; silane coupling agent classes such as gamma-amino propyl trimethoxy silicane; sec.-propyl three isostearoyl base titanic acid ester; sec.-propyl three (dioctylphyrophosphoric acid) titanic acid ester; titanic acid ester coupler classes such as sec.-propyl three decyl Phenylsulfonic acid titanic acid ester; aluminium coupler classes such as ethanoyl aluminum alkoxide diisopropyl acid esters etc.

The surface-treated method has damp process and drying process.Damp process is that above-mentioned surface treatment agent is joined with aqueous or emulsion form in the slurry of hydrotalcite-based compound of the present invention, stirs down in until about 100 ℃ of temperature thorough mixing.In addition, drying process is the surface treatment agent of aqueous, emulsion form or solid state to be added in the powder of hydrotalcite-based compound of the present invention with mixing machines such as Henschel mixers to go, as long as thorough mixing, and heating or do not heat all right.Also have, the usage quantity of surface treatment agent is being that about 0.1～about 15 weight % serve as preferred with respect to hydrotalcite-based compound of the present invention.

Hydrotalcite-based compound of the present invention or through the occasion of this surface-treated compounds as infrared absorbent, consider from machinability and the dispersiveness resin, with the average aggregate particle size measured with the laser diffraction and scattering method below 5 μ m and the BET specific surface area at 30m ²/ g is following to be preferred.Also having, be preferably below 1 μ m by the average primary particle diameter of the seen hydrotalcite-based compound of electron microscope, more preferably, preferred especially below the 0.3 μ m below the 0.5 μ m.Shape serves as preferred with tabular (comprising that sexangle is tabular), and the big person of length-to-diameter ratio (=tabular planar mean diameter/mean thickness) is preferred.

Agricultural film of the present invention for example has polyolefin resin, chloride resinoid, polyester resin, acrylic resin, fluorinated resin etc. with thermoplastic resin.The above-mentioned polyolefin resin that can enumerate has, for example, low density, the homopolymer of alpha-olefins such as high-density or straight chain shaped polyethylene and polypropylene, ethylene-propylene copolymer, ethene-1-Butylene copolymer, ethene-4 methyl 1 pentene copolymer, ethene-hexene copolymer, the multipolymer of alpha-olefins such as ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, the ethylene-methyl methacrylate methyl terpolymer, ethylene-vinyl acetate-methylmethacrylate copolymer, alpha-olefins such as ionomer resin are the alpha-olefin of main component and the monomeric multipolymer beyond the alpha-olefin.The synthetic used catalyzer of these polyolefin resins has, for example, and Ziegler-natta catalyst, chromium class catalyzer, single position (singlesite) class catalyzer (metallocene class catalyzer) etc.Synthetic method has solution method, vapor phase process etc., also has high-pressure process, low-pressure process, non-pressure process etc., but to this not special restriction.Chloride resinoid has, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinatedpolyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinylchlorid-styrol copolymer, vinylchlorid-isobutylene copolymers, vinylchlorid-butadienecopolymer, vinylchlorid-isoprene copolymer, vinylchlorid-chloropropene multipolymer, vinylchlorid-maleate copolymer, vinylchlorid-alkylmethacrylate polymer, vinyl chloride-acrylonitrile copolymer, vinylchlorid-styrene-maleic anhydride copolymer, vinylchlorid-styrene-acrylonitrile copolymer, vinylchlorid-vinylidene chloride-vinyl acetate copolymer, vinylchlorid-various vinyl ether co-polymers etc.; Vibrin is enumerated poly-para Toluic Acid's glycol ester, poly-para Toluic Acid's butanediol ester, poly-naphthoic acid butanediol ester, polyether polyester etc.; Fluoro-resin has tetrafluoroethylene etc.Can separately and mix these resins that use institute's example more than 2 kinds.

Can also be engaged in various additives habitual in the present technique in the agricultural film of the present invention.The example of such additive has photostabilizer, anti-turbid dose, antifogging agent, oxidation inhibitor, UV light absorber, softening agent, static inhibitor, lubricant, thermo-stabilizer, fluorescent agent, anti, pigment, dyestuff, antiseptic-germicide, mould inhibitor, releasing agent, plateout to prevent agent, processing aid etc.Also have, also can merge and use with other infrared absorbent.Merge to use these various additives, the persistence that just can obtain weathering resistance, anti-turbid property, antifog property, dirt resistance, anti-drop property, toughness, resistance to pesticide, acidproof rain, thermotolerance, fading property, germ resistance, mildew resistance, the open operation of stretching, extension and prevent all excellent and these characteristics of the resin aged performance that is caused by various additives is the agricultural film of excellence also.

Photostabilizer can be enumerated hindered amine compound, cresols class, melamine class, M-nitro benzoic acid etc., but generally to use hindered amine compound for well, preferably molecular weight more than 250 at 2 of 4-substd, 2,6,6-tetraalkyl piperidine derivative is preferred, and the substituting group of its 4-position is enumerated carboxylic acid group, alkoxyl group, alkylamino etc.Also have, replace at N-position alkyl.The object lesson of such hindered amine compound has, the TINUVIN492 of the compound shown in following formula (a)～(t) and チバガイギ-company, and 494 grades contain hindered amines stablizer etc.

The addition of such photostabilizer is being 0.02～5 weight % with respect to thermoplastic resin, and 0.1～2 weight % is preferred, can separately or merge use more than 2 kinds.

Specifiable anti-turbid dose has nonionic class, anionic species, cationic tensio-active agent.For example, the ester of the epoxide affixture of the ester of polyoxy alkylidene ether, polyvalent alcohol or part ester, polyvalent alcohol or part ester, higher alcohol sulfate an alkali metal salt, alkyl aryl sulfonic acid ester, quarternary ammonium salt, fatty amine derivative.That specifically enumerates has: the polyethylene oxide laurate, polyethylene oxide stearyl ether, the polyethylene oxide nonylplenyl ether, the polyoxyethylene glycol monopalmitate, polyethylene glycol mono stearate, the polyethylene oxide Span-20, the polyethylene oxide sorbitan monopalmitate, glycerol, tetramethylolmethane, Sorbitol Powder, one contract polyvalent alcohol and lauric acid such as two glycerol or triglycerin, palmitinic acid, the ester of aliphatic carboxylic acid such as stearic acid or oleic acid or part ester, Sodium Lauryl Sulphate BP/USP, Sodium dodecylbenzene sulfonate, sodium butylnaphthalenesulfonate, palmityl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, the dodecyl amine hydrochlorate, the amino ethyl ester of phosphoric acid lauric acid lauroyl, triethyl hexadecyl ammonium iodide, the amino diethylamide hydrochlorate of oleoyl, dodecyl pyridine ] the alkaline pyridine  of vitriol] salt etc.

Anti-turbid dose addition like this is for being 0.2～5 weight % with respect to thermoplastic resin, and 0.5～3 weight % be preferred, separately or merge use more than 2 kinds and all can.

The antifogging agent of enumerating has, and for example, the fluorine cpd (fluorine class tensio-active agent) of perfluoroalkyl, ω-hydrofluoroalkane base etc. is arranged, and also has the silicon compounds (silicon class tensio-active agent) of alkyl siloxy etc.

The addition of such antifogging agent is 0.01～5 weight % with respect to thermoplastic resin, and 0.02～2 weight % is preferred, separately or merge more than 2 kinds to use and all can.

The oxidation inhibitor of enumerating has phenols, Phosphorus, sulphur class, azanol class etc., also has, and also can use at the piperidines shown in the photostabilizer etc.The object lesson of phenolic antioxidant has: 2; 6-two uncles (-シヤ Le) butyl p-cresol; Thiovanic acid stearyl--(3; 5-dimethyl-4-hydroxybenzyl) ester; propionic acid stearyl--β-(4-hydroxyl-3; the 5-di-tert-butyl-phenyl) ester; phosphonic acids distearyl acyl group-3; 5-di-tert-butyl-4-hydroxyl benzyl ester; 2; 4; 6-three (3 '; 5 '-di-t-butyl-4 '-hydroxybenzyl sulphur)-1; 3; 5-three azines; propanedioic acid distearyl acyl group-(the 4-hydroxy-3-methyl-5-tertiary butyl) benzyl ester; 2; 2 '-methylene radical two (4-methyl-6-tert butyl phenolic group); 4; 4 '-methylene radical two (2; 6-di-t-butyl phenolic group); 2; 2 '-methylene radical two [6-(1-methylcyclohexyl) p-cresol]; two [3; 5-two (4-hydroxyl-3-tert-butyl-phenyl) butyric acid] glycol ester; 4; 4 '-butylidene two (6-tertiary butyl meta-cresol); 2; 2 '-ethylene (4; the 6-di-tert-butylphenol); 1; 1; 3-three (2-methyl-4-hydroxyl-5-tertiary butyl phenolic group) butane; terephthalic acid two [the 2-tertiary butyl-4-methyl-6-(the 2-hydroxyl-3-tertiary butyl-5-methyl-benzyl) phenyl] ester; isocyanic acid 1; 3; 5-three (2; 6-dimethyl-3-hydroxyl-4-tertiary butyl) benzyl ester; 1; 3; 5-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl)-2; 4; the 6-Three methyl Benzene; 2; 6-phenylbenzene-4-octadecane oxygen base phenol; four [methylene radical-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane; isocyanic acid 1; 3; 5-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) ester; isocyanic acid 1; 3; 5-three [(3; the 5-di-tert-butyl-hydroxy phenyl) propoxy-ethyl] ester; 2-octyl group-4; 6-two (4-hydroxyl-3; the 5-di-t-butyl) phenol oxygen-1,3,5-three azines; 4; 4 '-sulfo-two phenols and 4 such as (6-tertiary butyl meta-cresols); 4 '-(for example the polymerization degree is 2,3,4 for the carbonate oligomer ester of butylidene two (the 2-tertiary butyl-5-methylphenol); 5; 6,7,8; 9,10 etc.) etc. polyphenol carbonate oligomer ester class.

What Phosphorus oxidation inhibitor specifically can be enumerated has: triphenylphosphate; tricresyl phosphate (nonyl phenyl) ester; tricresyl phosphate (to the nonyl phenyl) ester; tricresyl phosphate (to phenyl) ester; tricresyl phosphate (adjacent dicyclohexyl phenyl) ester; tricresyl phosphate (single nonyl/dinonyl phenyl) ester; the phosphoric acid phenyl is to the nonyl phenylester; tricresyl phosphate (2; the 4-di-tert-butyl-phenyl) ester; triaryl phosphates such as tricresyl phosphate [the 2-tertiary butyl-4-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl sulphur)-5-aminomethyl phenyl] ester; mono phosphoric acid ester octyl group diphenyl; the single phenylester of di(2-ethylhexyl)phosphate octyl group; phosphoric acid didecyl base mono-phemyol ester; alkyl aryl phosphates such as mono phosphoric acid ester decyl phenyl phenylester; tributyl phosphate; trioctyl phosphate; tridecyl phosphate; tricresyl phosphate lauroyl ester; trialkylphosphates such as tricresyl phosphate oleoyl ester; bisphosphate two (three decyls) pentaerythritol ester; bisphosphate two hard ester acyl group pentaerythritol esters; bisphosphate two (nonyl phenyl) pentaerythritol ester; bisphosphate two (2; the 4-di-tert-butyl-phenyl) pentaerythritol ester; bisphosphate two (2; 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol ester; bisphosphate four (three decyls) isopropylidene hexichol phenolic ester; triphosphoric acid six (three decyls)-1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane ester; bisphosphate four (2; the 4-di-tert-butyl-phenyl) diphenylene ester; phosphoric acid 2; 2 '-organophosphorus acids such as methylene radical two (4, the 6-di-tert-butyl-phenyl) octyl group ester with alkyl is arranged; aryl; the organic phosphoric acid metal salt compound of the compound of the organic and phosphate metal salt of alkaryl or ehter bond etc.

The sulfur type antioxidant of enumerating has: the ester of the polyvalent alcohol of the alkyl sulfide propionic acid of the dialkyl group thiodipropionic acid ester of two bay acyl groups, distearyl acyl group etc. and butyryl radicals, capryloyl, lauroyl, stearyl-etc. (for example glycerol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, trihydroxy-ethyl isocyanate) etc., that specifically enumerates has two bay acyl group thiodipropionic acid esters, distearyl acyl group thiodipropionic acid ester, tetramethylolmethane four lauroyl sulphur propionic esters etc.

The addition of such oxidation inhibitor is 0.01～5 weight % with respect to thermoplastic resin, and 0.02～3 weight % is preferred, separately or merge more than 2 kinds to use and all can.

The UV light absorber of enumerating has benzotriazole category, benzophenone, salicylate class etc.The benzotriazole category object lesson of enumerating is: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) benzotriazole, 2-(2 '-methyl-4 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-methyl-5 '-tert-butyl-phenyl) benzene opens triazole, (2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl)-5-methoxyl group benzo triazole, 2-(2 '-Octadecane oxygen base-3 ', 5 '-3,5-dimethylphenyl)-the 5-Methylbenzotriazole, 2-(2 '-hydroxyl-5 '-p-methoxy-phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-p-methoxy-phenyl)-the 5-Methylbenzotriazole, 2-(2 '-hydroxyl-5 '-p-methoxy-phenyl)-5,6-dichloro benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-dichloro hexyl phenyl) benzotriazole, 2-(2 '-hydroxyl-4 ', 5 '-dichlorophenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-aminomethyl phenyl)-5-butoxy carbonyl benzotriazole, 2-(2 '-hydroxyl-4 ', 5 '-3,5-dimethylphenyl)-5-butoxy carbonyl benzotriazole, 2-(2 '-hydroxyl)-5-ethoxycarbonyl benzotriazole, 2-(2 '-acetoxyl group-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5-ethyl sulfonyl benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl)-5-ethyl sulfonyl benzotriazole, 2-(2 '-hydroxyl-5 '-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminophenyl) benzotriazole.

The benzophenone of specifically enumerating has: 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-positive 12-alkoxy benzophenone, the positive 18 oxygen base benzophenone of 2-hydroxyl-4-, 2-hydroxyl-4-benzyloxy benzophenone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2-hydroxyl-4-methoxyl group-5-sulfo-benzophenone, 2-hydroxyl-5-chlorobenzophenone, 2, the 4-dihydroxy benaophenonel, 2,2 '-dihydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-5-sulfo-benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone etc.

The salicylate class of specifically enumerating has: salol, p-t-butylphenyl salicylate, Whitfield's ointment are to methyl phenyl ester, p-octylphenyl salicylate etc.

Also have the 2-of the triazines of enumerating that other are arranged (4,6-phenylbenzene-1,3,5-three azines-2-yl)-5-[(hexyl) oxygen] phenol and oxalic acid anilide class 2-oxyethyl group-2 '-ethyl oxalic acid two anilides etc.

The addition of such UV light absorber, with respect to 0.01～3 weight % of thermoplastic resin, and 0.05～2 weight % is preferred, separately or merge more than 2 kinds to use and all can.

Can use plastifying common plasticizers such as polyvinyl chloride and alkene-vinyl alcohol-based copolymer as softening agent.For example, low-molecular-weight polyalcohols, phthalate, phosphoric acid ester, aliphatics monobasic acid ester class, epoxy compounds, paraffinic etc.

The low-molecular-weight polyvalent alcohol of specifically enumerating is glycerol, ethylene glycol, triethylene glycol, Sorbitol Powder etc.

The phthalate of specifically enumerating is dimethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), Di Iso Decyl Phthalate, O-phthalic heptyl heptylate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, O-phthalic acid butyl lauroyl ester, MOP etc.

The phosphoric acid ester of specifically enumerating has: tritolyl phosphate, trixylyl phosphate, di(2-ethylhexyl)phosphate xylyl list cresols ester, mono phosphoric acid ester xylyl diformazan phenolic ester, tributyl phosphate, triphenylphosphate, tricresyl phosphate-2-(ethyl hexyl) ester etc.

The aliphatics monobasic acid ester class of specifically enumerating has: butyl oleate, glycerol monoleate, butyl stearate, diisodecyl adipate, Polycizer W 260, Octyl adipate, hexanodioic acid isodecyl ester, dioctyl azelate, di-2-ethylhexyl adipate, ethanoyl methyl ricinoleate etc.

The epoxy compounds of specifically enumerating is the epoxy compounds same with the thermo-stabilizer of saying later.

The paraffinic of specifically enumerating has: chloroalkane hydrocarbon, Butyryl Chloride are for paraffinic hydrocarbons, mobile paraffinic hydrocarbons etc.

The addition of such softening agent is 1～70 weight % with respect to thermoplastic resin, and 2～60 weight % are preferred, separately or merge more than 2 kinds to use and all can.

The antistatic agent of enumerating is non-ionic type or cationic surfactant etc.Specifically enumerate polyethylene oxide, carbowax, pentaerythritol monostearate, sorbitan monopalmitate, polyethylene oxide alkylamine, polyglycol ether are arranged, to styryl sodium sulfonate etc.

The addition of such antistatic agent is 0.01～5 weight % with respect to thermoplastic resin, and 0.02～3 weight % is preferred, separately or merge more than 2 kinds to use and all can.

The lubricant of enumerating has fatty acid, fatty acyl amide, ester class, wax, paraffinic hydrocarbons etc., and what specifically enumerate is stearic acid, palmitinic acid, tetradecanoic acid, stearylamide, palmitic amide, mustard acid amides, methylene radical distearyl acid amides, ethylene bis stearamide, butyl stearate, butyl palmitate, polyethylene wax, mobile paraffinic hydrocarbons etc.

The addition of such lubricant is 0.01～5 weight % with respect to thermoplastic resin, and 0.05～3 weight % is preferred, separately or merge more than 2 kinds to use and all can.

Have as thermo-stabilizer: mineral-type, organic acid metal salt, organic acid composition metal salt, organic tin, epoxy compounds class, many alcohols, sulphur class, antimony organic class, phosphoric acid ester, beta-diketon class, nitrogenous class etc.

The mineral-type thermo-stabilizer of specifically enumerating has: the salt of the oxygen acid of halogens such as the metal oxide of Li, Na, K, Mg, Ca, Sr, Ba, Pb, Zn, Cd, Zr, Al, Sn, Sb, Bi etc., oxyhydroxide, carbonate, vitriol, phosphoric acid salt, phosphite, silicate and these metals and perchloric acid, Periodic acid, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, chlorous acid, hypochlorous acid, bromous acid etc.

The organic acid metal salt heat stabilizers has above-mentioned metal and following organic acid acid salt, neutral salt, subsalt, concrete organic acid has: 2 ethyl hexanoic acid (acid of 2-エチ Le ヘキソイ Application), lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oxystearic acid, linolenic acid, mountain Yu acid, Unimac 5680, oleic acid, ricinoleate acid, caproic acid, enanthic acid, just or isocaprylic acid, n-nonanoic acid, capric acid, isodecyl acid, undecanoic acid, new three capric acid, acetoacetic acid, aliphatic carboxylic acids such as acetic acid, toxilic acid, thio-2 acid, diprotic acid such as two thiodipropionic acids, this diprotic acid and replacement or unsubstituted aliphatics, the diprotic acid partial esterification thing of alicyclic or aromatic alcohols, M-nitro benzoic acid, benzoin methyl acid, the butyl M-nitro benzoic acid, to tertiary butyl M-nitro benzoic acid, phenyl acetic acid, Whitfield's ointment, fumaric acid, naphthoic acid, sylvic acid, phenyl stearic acid, the indenyl carboxylic acid, styracin, roseolic acid, ring-type organic acids such as naphthenic acid etc.

Organic composition metal salt heat stabilizers of specifically enumerating has: above-mentioned organic acid Ca/Zn class, Ba/Cd class, Ba/Zn class, Ba/Cd/Zn class.

The organic tin thermo-stabilizer of specifically enumerating has: single (or two) methyl or butyl or tin octylate three (or two) laurate, the polymkeric substance of single (or two) methyl or butyl or tin octylate maleic acid ester, single (or two) methyl or butyl or tin octylate three (or two) iso-octyl maleic acid ester, single (or two) methyl or butyl or tin octylate mercaptoacetate, single (or two) methyl or butyl or tin octylate-2 mercaptopropionic acid ester, single (or two) methyl or butyl or tin octylate three (or two) dodecyl mercapto-carboxylic ester, single (or two) methyl or butyl or tin octylate sulfuric ester, single (or two) methyl or butyl or tin octylate mercaptoacetate, single (or two) methyl or butyl or tin octylate three (or two) 2-sulfydryl second oleic acid ester, sulfo-two (oleic acid monomethyl tin two-2-sulfydryl ethyl ester), sulfo-two (oleic acid dimethyl or butyl or tin octylate list-2-sulfydryl ethyl ester) etc.

The epoxy compounds type thermal stabilizing agent of specifically enumerating has: epoxidised soybean oil and its diacetyl direactive glyceride; epoxidised linseed oil; the epoxidised linseed oil fatty acid butyl ester; epoxidation 1; the 2-polyhutadiene; dihydroxyphenyl propane-diglycidylether; 3; 4-epoxycyclohexyl methyl; 3; 4-epoxycyclohexyl carboxylicesters; the epoxidation tallow oil; the epoxidation Oleum Gossypii semen; epoxidation sunflower oil; epoxidation tolu oil; epoxidation fish oil; epoxidation ethanoyl alkene; methyl epoxidation stearic acid; butyl epoxidation stearic acid; iso-octyl epoxidation stearic acid; 2-ethylhexyl epoxidation stearic acid; isodecyl epoxidation stearic acid; the cyclohexyl ring ketostearic acid; dihydro nonyl epoxidation stearic acid; methoxy ethyl epoxidation stearic acid; acetoxyl group ethyl epoxidation stearic acid; benzoyl epoxidation stearic acid; tetrahydrofuran base epoxidation stearic acid; the benzyl ring ketostearic acid; to tert-butyl-phenyl epoxidation stearic acid; butyl epoxy tolu fatty acid oil; n-octyl epoxy tolu fatty acid oil; iso-octyl epoxy tolu fatty acid oil; 2-ethylhexyl epoxy tolu fatty acid oil; epoxidation ethanoyl glyceryl monoricinoleate; 3; 9 of 4-epoxycyclohexyl methyl alcohol; the 10-epoxy stearate; 3; 9 of 4-epoxycyclohexyl methyl alcohol; 10; 12; 13-diepoxy stearate; 3; the 2-ethyl-1 of 4-epoxycyclohexyl carboxylic acid; 3-hexyl diol ester; the dialkyl group of epoxy hexahydrophthalic acid (for example; di-n-butyl; di-n-hexyl; two-2-ethylhexyl; diisooctyl; two positive decyls; diiso decyl; di-n-butyl decyl etc.) ester; 3; 4-epoxy-6-methylcyclohexyl carboxylicesters; two (3,4-epoxy-6-methyl cyclohexane ylmethyl) caproic acid; the condenses of epoxyhalopropane and dihydroxyphenyl propane etc.

The how pure type thermal stabilizing agent of specifically enumerating has: tetramethylolmethane, mannitol, xylyl alcohol, Sorbitol Powder, glycerol, TriMethylolPropane(TMP), polyoxyethylene glycol, polyvinyl alcohol, 1,3-butyleneglycol, propylene glycol, dipropylene glycol, ethylene glycol, Diethylene Glycol, neopentyl glycol, trihydroxyethyl methane, two glycerol, two TriMethylolPropane(TMP)s, two trimethylolethanes, two-, three-, four-tetramethylolmethane, three (hydroxyethyl) isocyanic ester etc., and organic acid such as these many alcohol and aliphatic carboxylic acid, aromatic carboxylic acid, amino acid, alcohol acid and its part ester etc.The organic acid that forms above-mentioned part ester specifically has: sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, Unimac 5680, oxystearic acid, oleic acid, monobasic aliphatic carboxylic acids such as ricinoleate acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, phthalic acid, toxilic acid, fumaric acid, methylene-succinic acid, thio-2 acid, dibasic aliphatic carboxylic acids such as dithio propionic acid, M-nitro benzoic acid, benzoin methyl acid, aromatic carboxylic acids such as Whitfield's ointment, glycine, L-Ala, leucine, phenylalanine, methionine(Met), aspartic acid, L-glutamic acid, amino acid such as Trimethyl glycine, lactic acid, citric acid, tartrate, alcohol acids such as oxysuccinic acid.

The sulphur type thermal stabilizing agent of specifically enumerating has: thiodipropionate, 6-anilinos (エニリノ)-1 such as two lauroyl thiodipropionates, distearyl thiodipropionate, lauroyl stearyl thiodipropionate, 3,5-three azines-2, mercaptan carboxylic acid anhydride such as three azine mercaptan such as 4-two mercaptan, mercaptan lauric anhydride etc.

The antimony organic type thermal stabilizing agent of specifically enumerating has: single (or two) methyl or single (or two) alkyl antimony such as butyl or octyl group antimony three (or two) laurate laurate class, single (or two) methyl or butyl or octyl group antimony maleic acid ester polymkeric substance, single (or two) alkyl antimony such as single (or two) methyl or butyl or octyl group antimony three (or two) iso-octyl maleic acid ester maleic acid esters (class of マレエ-ト), single (or two) methyl or butyl or octyl group antimony three (or two) iso-octyl THIOGLYCOL acid esters, single (or two) methyl or butyl or octyl group antimony three (or two) THIOGLYCOL acid esters (or 2 mercaptopropionic acid ester), single (or two) methyl or butyl or octyl group antimony three (or two) dodecyl mercapto-carboxylic ester, single (or two) methyl antimony sulfuric ester, dioctyl antimony sulfuric ester, two (dodecyl) antimony sulfuric ester, single (or two) methyl or butyl or octyl group antimony three (or two)-2-mercaptoethyl oleic acid ester, sulfo-two [monomethyl antimony two (2-mercaptoethyl oleic acid ester)], single (or two) alkyl antimony such as sulfo-two [dimethyl or butyl or octyl group antimony two (2-mercaptoethyl oleic acid ester)] mercapto-carboxylic ester class etc.

It is the same with Phosphorus oxidation inhibitor that the phosphoric acid ester thermo-stabilizer is enumerated.

The beta-diketon type thermal stabilizing agent of specifically enumerating has: methyl aceto acetate; dehydro-acetic acid; methyl ethyl diketone; benzoyl acetone; benzoyl propenyl methane; phenyl phenacyl ketone; stearoyl benzoyl methane; trifluoroacetylacetone; dehydro-acetic acid propylene ester; the dehydrobenzene formyl acetic acid; cyclohexyl-1; the 3-diketone; 1; 1-dimethyl cyclohexane-3; 5-diketone (dimethone); 2; 2-methylene radical cyclohexyl-1; the 3-diketone; 2-benzyl rings hexyl-1; the 3-diketone; acetyl benzo pimelinketone; palmityl benzo pimelinketone; stearyl benzo pimelinketone; benzoyl benzo pimelinketone; 2-acetyl pimelinketone; 2-benzoyl pimelinketone; 2-acetyl cyclohexyl-1; the 3-diketone; benzoyl is to chlorobenzoyl methane; two (4-toluyl) methane; two (2-(2-hydroxybenzoyl)) methane; benzoyl acetyl methane; tribenzoylmethane; diacetyl benzene formyl methane; palmityl benzoyl methane; lauroyl benzoyl methane; 4-methoxybenzoyl benzoyl methane; two (4-methoxybenzoyl) methane; two (4-chlorobenzoyl) methane; two (3,4-methylenedioxy benzene formyl) methane; benzoyl acetyl octyl group methane; benzoyl phenyl methyl ketone methylmethane; stearyl-4-methoxybenzoyl methane; two (4-tert.-butylbenzene formyl) methane; benzoyl acetyl ethyl methane; benzoyl trifluoroacetyl methane; diacetyl methane; butyryl acetyl methane; oenanthyl acetyl methane; triacetyl methane; distearyl methane; stearyl acetyl methane; palmityl acetyl methane; lauroyl acetyl methane; benzoyl formyl methane; acetyl formyl methane; benzoyloxy phenyl acetyl methane; two (hexamethylene acyl) methane; two pivalyl methane etc. and the Li that contains these compounds; Na; Mg; Ca; Ba; Sr; Zn; Al; Zr; the metal-salt of the metal of Sn etc. etc.

The nitrogenous type thermal stabilizing agent of specifically enumerating has: thiambutosine, stearyl alcohol, cetyl alcohol, 1, beta-amino crotonate, 2-phenylindone, the dihydro-1 of the alcohols of 3-butyleneglycol, thio-diethylene glycol etc., 4-dimethyl-2,6-two carbonization didecyl oxygen bases-3,5-pyridine etc.

The addition of such thermo-stabilizer is 0.001～10 weight % with respect to thermoplastic resin, and 0.005～5 weight % is preferred, separately or merge more than 2 kinds to use and all can.

The fluorescent agent of enumerating has: violanthrone dye class, isoviolanthrone dye class, perillene class (ペリレ Application), thioxanthene class, coumarins, anthraquinone class, benzo pyran, naphthalimide class or naphthalic acid class, benzopyrazines class, pyrazine class, cyanopyrazine class, stilbene class, diamino hexichol class, imidazoles, imidazolone, triazole species, thiazoles,  azole, quinolones, pyrazolines, dihydropyridines etc.

The addition of such fluorescent agent is 0.001～10 weight % with respect to thermoplastic resin, and 0.01～5 weight % is preferred, separately or merge more than 2 kinds to use and all can.

At last, other infrared absorbents that can enumerate have: the oxyhydroxide of silicon-dioxide and silicate, lithium, calcium, magnesium, aluminium or oxide compound, aluminate, borate or vitriol, known hydrotalcite-based compound etc., they separately or merge more than 2 kinds to use and all can.But, because maintain A negatively charged ion of the present invention and the anionic hydrotalcite-based compound of B, have excellent infrared ray absorption ability and can give excellent light trafficability characteristic again, so preferred independent the use with the occasion that is contained in the agricultural film.

With respect to the used thermoplastic resin of for example agricultural film, the addition of infrared absorbent can be, thing of the present invention separately or with the total amount of other infrared absorbents be 1～30 weight %.When infrared rays absorption agent less than 1 weight %, can not give full play to the effect of infrared absorbent, and the ultraviolet and the visible light trafficability characteristic of agricultural film descends with physical strength when surpassing 30 weight %, thus improper.

Also have, in the time of in be included in the thermoplastic resin that agricultural film uses as infrared absorbent with hydrotalcite-based compound of the present invention and when film shaped, occur sometimes foaming and problems such as flake, this will use the material of removing middle water as required.

Can mix according to usual method, for example, can use Henschel mixing tank, high-speed mixer, ribbon blender etc. that resin, infrared absorbent and other additive are mixed, then pinch machine etc. and carry out fusion and mix with Banbury muller, the forcing machine that mixes, pressure.Secondly, be formed film, can be with blow-moulding process for example, extrude usual method such as the film shaped method of T shape die head and carry out.

Also have, the used agricultural film of the present invention is not only individual layer, also can use multilayer film.The formation of multilayer film is enumerated a kind of two layers, a kind of three layers, two kinds two layers, two kinds three layers, three kinds three layers, three kinds four layers, three kinds five layers, four kinds four layers, four kinds five layers, five kinds five layers etc., and the kind of the thermoplastic resin of each layer or the thermoplastic resin of blend also can be different.From the heat retaining property angle, preferably the hope selection is at least a in the thermoplastic resin has the resin of good absorption at wavelength 2.5 μ m～25 μ m.Also have, the additive in each layer should can make up cooperation according to the suitably selection that is used for of each layer.Other as the method for the anti-turbid property that keeps film for a long time, except the above-mentioned method that cooperates, can also adopt the method that forms anti-turbid property epithelium at least at the inner face of unfolded agricultural films such as agricultural greenhouse in film.

Below and comparative example come together to illustrate embodiments of the invention, but, the present invention is not limited in these examples.

About the hydrotalcite-based compound of in embodiment and comparative example, making, at first carry out the evaluation of hydrotalcite-based compound with XRD method.Then, use the analytical value of the metallic cation that obtains by the compositional analysis method to calculate basic layer mol ratio (X, y1, y2), and calculate the mol ratio (Z2) of B negatively charged ion basic layer by the anionic analytical value of B.Also { (B) the total valence mumber of negatively charged ion (X) the substitution formula that determines by basic layer _Z2Total valence mumber/X=} calculate the shared ratio of the anionic total valence mumber of B.When the A negatively charged ion is the oxygen acid radical ion of silicon class, Phosphorus or boron class, by consider ion-exchange they the time used raw material, the Si that obtains by compositional analysis and P, B analytical value and the interplanar distance of (002) or (003) face of obtaining by xrd method and the measurement result of infrared absorption spectrum etc., come to contain in the oxygen acid radical ion of the silicon class between prediction interval, Phosphorus or boron class and still do not contain and how to contain poly oxygen acid radical ion.Judge that it is difficult that silicon class, oxygen acid radical ion Phosphorus or the boron class remain on interlayer with which type of form; Also have, in these oxygen acid radical ions, also comprise the poly oxygen acid of one or more H bases and OH base and different polymerization degree, be specific these valence mumber also be difficult.In an embodiment, for the composition formula of the oxygen acid radical ion of convenient expression silicon class, Phosphorus or boron class, with (polymer Si _mO _2m+1), (polymer P _mO _(5m/2)+1), (polymer B _mO _(3m/2)+1) represent that all draw the valency as 2-in the calculating of composition formula.Also have, Si and P, B are compositional analysis value substitution formula { (mole number of Si+P+B)/(Al by separately to the mol ratio of Al ₂O ₃Mole number)=calculate.In addition, try to achieve the numerical value of specific surface area with the BET method by the adsorptive capacity of nitrogen, average aggregate particle size is represented powder is joined the numerical value that is recorded by the laser diffraction and scattering method in the organic solvent behind ultra-sonic dispersion.

Again, measure dispersiveness and the insulation index of film, total light penetration and the haze value (turbidity) of infrared absorbent in film for the film of the infrared absorbent that contains embodiment and comparative example.Also have, judge the dispersiveness (generation of spending) of infrared absorbent in film with range estimation.The insulation index is to measure the infrared ray absorption rate of each wavelength and calculated by the described method in back with the infrared absorption spectrometry device.Also have, the light trafficability characteristic is measured by turbidometer, and it is with total light penetration and haze value (turbidity) expression.

Ask insulation exponential method to be, the blackbody radiation of being obtained each wavelength by following formula (3) can (E λ d λ), to 400cm ^-1～2000cm ^-1Blackbody radiation can integration (∑ (E λ d λ)) be used as the energy density of total blackbody radiation.Then measure the infrared ray absorption rate of (containing infrared absorbent) film, can (E λ d λ) be used as total absorption energy density of this film with the infrared ray absorption rate integration of each wavelength by the blackbody radiation of each wavelength at each wavelength by the infrared absorption spectrometry device.So the ratio (following formula (6)) that total blackbody radiation energy density and film is always absorbed energy density is as the insulation index.

Eλ·dλ＝2πhC^2/[λ^5{e^(hC/λkT)-1}]·dλ ……(3)

λ: wavelength; H: quantum of action; C: the very aerial light velocity;

K: Boltzmann constant; T: absolute temperature

Insulation index=(always absorbing energy density/total blackbody radiation energy density) * 100 (6)

The insulation exponential numerical value that is calculated by the aforementioned calculation formula is big more, means that its infrared ray absorption ability is high more, means that promptly heat retaining property is good more.Also have, the total light penetration value that is obtained by turbidometer approaches 100 more and means that its visible light permeability is good more, and the more little meaning of mist degree (turbidity) numerical value is less muddy.

Embodiment 1

The MgCl of 2 liters of 1.5mol/l ₂The Al of solution and 0.667 liter of 1.0mol/l ₂(SO ₄) ₃The mixed solution of solution joins in the stainless steel vessel, under agitation injects 2.889 liters 3.0mol/l sodium hydroxide solution, keeps 30min.Then this reaction paste is moved into autoclave, 170 ℃ of hydrothermal treatment consists 6h.After the cooling, filter, wash.Then dehydrate is put into and is added 5 and lift away from the stainless steel vessel of sub-exchanged water, stir and make its slurryization once more, 90 ℃ heat after, stir down and add with SiO ₂The sodium silicate solution of 1.300 liters of 1.0mol/l of conversion (No. 3 water glass) stirs 2h.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer Si _4.84O _10.68) _0.062(SO ₄) _0.062(CO ₃) _0.0300.69H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.60, and Si is to Al ₂O ₃Mol ratio be 1.95.Also have, BET is 23m ²/ g, average aggregate particle size is 0.69 μ m.

Embodiment 2

After handling with method water glass similarly to Example 1, filter, wash, dehydrate is put into added 5 and lift away from the stainless steel vessel of sub-exchanged water, stir and make its slurryization once again, heat at 80 ℃.Measure 16.5g sodium stearate (purity 86%) more in addition, be dissolved in 80 ℃ of ion exchanged waters of heating.It is injected in the slurry of stirring, carries out surface treatment.At last, filter, washing, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer Si _4.84O _10.68) _0.062(SO ₄) _0.062(CO ₃) _0.0300.69H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.60, and Si is to Al ₂O ₃Mol ratio be 1.95.Also have, BET is 18m ²/ g, average aggregate particle size is 0.77 μ m, the surface treatment adsorptive capacity is 3.0 weight %.

Embodiment 3

The sample that obtains similarly to Example 2 at 200 ℃ of following thermal treatment 3h, is removed middle water.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer Si _4.84O _10.68) _0.062(SO ₄) _0.062(CO ₃) _0.0300.09H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.60, and Si is to Al ₂O ₃Mol ratio be 1.95.Also have, BET is 20m ²/ g, average aggregate particle size is 0.72 μ m, the surface treatment adsorptive capacity is 3.3 weight %.

Embodiment 4

The MgCl of 2 liters of 1.5mol/l ₂The Al of solution and 0.750 liter of 1.0mol/l ₂(SO ₄) ₃The mixed solution of solution joins in the stainless steel vessel, under agitation injects 3.000 liters 3.0mol/l sodium hydroxide solution, keeps 30min.Then this reaction paste is moved into autoclave, 170 ℃ of hydrothermal treatment consists 6h.Be cooled to below 100 ℃ the back and move in the stainless steel vessel, once more 80 ℃ heat after, stir down and add with SiO ₂The sodium silicate solution (No. 3 water glass) of 1.125 liters of 1.0mol/l that convert stirs 1h.Then, measure 14g stearyl phosphoric acid (purity 99%), be to suspend in 80 ℃ of diluted sodium hydroxide solutions of heating, join then in the slurry, carry out surface treatment, filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.

Analytical results is Mg _0.667Al _0.333(OH) ₂(polymer Si _6.02O _13.04) _0.0415(SO ₄) _0.095(CO ₃) _0.0300.43H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.75, and Si is to Al ₂O ₃Mol ratio be 1.50.Also have, BET is 15m ²/ g, average aggregate particle size is 0.70 μ m, the surface treatment adsorptive capacity is 3.0 weight %.

Embodiment 5

The sample that obtains similarly to Example 4 at 200 ℃ of following thermal treatment 3h, is removed middle water.

Analytical results is Mg _0.667Al _0.333(OH) ₂(polymer Si _6.02O _13.04) _0.0415(SO ₄) _0.095(CO ₃) _0.0300.08H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.75, and Si is to Al ₂O ₃Mol ratio be 1.50.Also have, BET is 18m ²/ g, average aggregate particle size is 0.68 μ m, the surface treatment adsorptive capacity is 3.3 weight %.

Embodiment 6

The MgCl of 2 liters of 1.5mol/l ₂The Al of solution and 0.698 liter of 1.0mol/l ₂(SO ₄) ₃The mixed solution of solution joins in the stainless steel vessel, under agitation injects 2.930 liters 3.0mol/l sodium hydroxide solution, keeps 30min.Then this reaction paste is moved into autoclave, 170 ℃ of hydrothermal treatment consists 6h.After the cooling, filter, wash.Then dehydrate is put into and is added 5 and lift away from the stainless steel vessel of sub-exchanged water, 90 ℃ heat after, stir down and add with SiO ₂The sodium silicate solution (No. 3 water glass) of 1.605 liters of 1.0mol/l that convert stirs 3h.Then measure 18.6g stearyl phosphoric acid ester (purity 99%), after suspending in the diluted sodium hydroxide solution of heating, join in the slurry, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Mg _0.683Al _0.317(OH) ₂(polymer Si _4.26O _9.52) _0.0855(SO ₄) _0.050(CO ₃) _0.0230.11H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.46, and Si is to Al ₂O ₃Mol ratio be 2.30.Also have, BET is 19m ²/ g, average aggregate particle size is 0.62 μ m, the surface treatment adsorptive capacity is 4.3 weight %.

Embodiment 7

The Mg of 3 liters of 2.0mol/l (OH) ₂Slurry joins in the stainless steel vessel, under agitation injects 0.750 liter 2.0mol/l Al (NO ₃) ₃Solution stirs 30min.Then this reaction paste is moved into autoclave, 170 ℃ of hydrothermal treatment consists 10h.After the cooling, filter, wash, then dehydrate is put in the stainless steel vessel that adds ion exchanged water, stir adding down with SiO ₂Behind the sodium silicate solution (No. 3 water glass) of 2.100 liters of 1.0mol/l that convert, heat for 90 ℃ and stir 2h.Then measure 17.8g stearyl phosphoric acid ester (purity 99%), after suspending in the diluted sodium hydroxide solution of heating, join in the slurry, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Mg _0.750Al _0.250(OH) ₂(polymer Si _3.17O _7.34) _0.1105(NO ₃) _0.005(CO ₃) _0.0120.06H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.12, and Si is to Al ₂O ₃Mol ratio be 2.80.Also have, BET is 16m ²/ g, average aggregate particle size is 0.68 μ m, the surface treatment adsorptive capacity is 3.3 weight %.

Embodiment 8

After the cooling of the slurry of hydrothermal treatment consists similarly to Example 1, after filtering, washing, dehydrate put into add 5 and lift away from the stainless steel vessel of sub-exchanged water, stir and make its slurryization once again, 90 ℃ heat after, stir down and add with SiO ₂The sodium silicate solution (No. 3 water glass) of the 0.967 liter of 1.0mol/l that converts and with SiO ₂Behind the sodium metasilicate solution of the 0.333 liter of 1.0mol/l that converts, stir 2h.Then measure 21.6g sodium stearate (purity 86%), after dissolving in the ion exchanged water of heating, join in the slurry under stirring, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer and monomer Si _3.37O _7.74) _0.089(SO ₄) _0.024(CO ₃) _0.0400.09H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.42, and Si is to Al ₂O ₃Mol ratio be 1.95.Also have, BET is 18m ²/ g, average aggregate particle size is 0.77 μ m, the surface treatment adsorptive capacity is 4.4 weight %.

Embodiment 9

After the cooling of the slurry of hydrothermal treatment consists similarly to Example 1, after filtering, washing, dehydrate is put in the stainless steel vessel that adds ion exchanged water, stir and make its slurryization once again, 80 ℃ heat after, stir the KH that adds 1.233 liters of 1.0mol/l down ₂PO ₄Solution also stirs 1h.Then measure 22.3g sodium stearate (purity 86%), after dissolving in the ion exchanged water of heating, join in the slurry under stirring, carry out surface treatment at 80 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer P _3.31O _9.275) _0.086(SO ₄) _0.020(CO ₃) _0.0480.09H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.44, and P is to Al ₂O ₃Mol ratio be 1.85.Also have, BET is 23m ²/ g, average aggregate particle size is 0.57 μ m, the surface treatment adsorptive capacity is 4.4 weight %.

Embodiment 10

The MgCl of 4 liters of 1.5mol/l ₂The Al of solution and 1.396 liters of 1.0mol/l ₂(SO ₄) ₃Solution mixing system becomes mixed solution.Also get the sodium carbonate solution of 1.0mol/l and the NaOH solution of 2.0mol/l in advance ready.MgCl ₂Solution and Al ₂(SO ₄) ₃The mixed solution of solution under agitation injects the successive reaction groove that has added ion exchanged water with 100ml/min, sodium carbonate solution continuously with the flow of 20ml/min, injecting NaOH solution simultaneously becomes 8～10 with conditioned reaction at pH and carries out, and the residence time at this moment is about 20min.Stable from reactant concn to get about 5.85 liters of reaction pastes the disposed slurry.Then the reaction paste of this taking-up after filtration, clean, wash at last with the sodium carbonate solution of about 2 liters of 0.5mol/l after, make it be suspended in 4.5 and lift away from the sub-exchanged water.This slurry is moved into autoclave, 170 ℃ of following hydrothermal treatment consists 12 hours.After the cooling, slurry is moved into stainless steel vessel stir the H that adds 0.928 liter of 1.0mol/l down ₃PO ₄Solution stirs 1h.80 ℃ heat after, measure 10.3g stearyl phosphoric acid ester (purity 99%), in the ion exchanged water of heating at 80 ℃ the dissolving after, join in the slurry, carry out surface treatment.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Mg _0.683Al _0.317(OH) ₂(polymer P _1.89O _5.725) _0.1115(CO ₃) _0.0470.11H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.30, and P is to Al ₂O ₃Mol ratio be 1.33.Also have, BET is 20m ²/ g, average aggregate particle size is 0.43 μ m, the surface treatment adsorptive capacity is 2.3 weight %.

Embodiment 11

After the slurry of hydrothermal treatment consists cools off similarly to Example 1, after filtering, washing, dehydrate is put in the stainless steel vessel that adds ion exchanged water, stir and make its slurryization once again, heating to stir down for 90 ℃ adds with SiO ₂The KH of the sodium silicate solution of 0.647 liter of 1.0mol/l of conversion (No. 3 water glass) and 0.647 liter of 1.0mol/l ₂PO ₄Solution also stirs 2h.Then measure 19.2g sodium stearate (purity 86%), after dissolving in the ion exchanged water of heating, join in the slurry under stirring, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer Si _3.36O _7.72) _0.0445(polymer P _3.36O _9.40) _0.0445(SO ₄) _0.042(CO ₃) _0.0230.11H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.42, and Si is to Al ₂O ₃Mol ratio be 0.97, P is to Al ₂O ₃Mol ratio be 0.97.Also have, BET is 20m ²/ g, average aggregate particle size is 0.80 μ m, the surface treatment adsorptive capacity is 3.9 weight %.

Embodiment 12

The MgCl of 1.75 liters of 1.5mol/l ₂The ZnCl of solution and 0.25 liter of 1.5mol/l ₂The Al of solution and 0.75 liter of 1.0mol/l ₂(SO ₄) ₃The mixed solution of solution joins in the stainless steel vessel, stirs the NaOH solution that injects 3.000 liters of 3.0mol/l down, keeps 30min.Then this reaction paste is moved into autoclave, 150 ℃ of hydrothermal treatment consists 1h.After cooling off then and filtering, wash, dehydrate is joined in the stainless steel vessel that adds ion exchanged water, stir make its once again slurryization and 90 ℃ heat after, stir the sodium tetraborate (Na that adds 0.469 liter of 1.0mol/l down ₂B ₄O ₇10H ₂O) solution stirs 2h.Continue, measure 20.9g sodium stearate (purity 86%), after dissolving in the ion exchanged water of heating, under agitation join in the slurry, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is (Mg _0.875Zn _0.125) _0.667Al _0.333(OH) ₂(polymer B _4.40O _7.60) _0.0945(SO ₄) _0.040(CO ₃) _0.0320.07H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.43, and B is to Al ₂O ₃Mol ratio be 2.50.Also have, BET is 16m ²/ g, average aggregate particle size is 0.66 μ m, the surface treatment adsorptive capacity is 4.5 weight %.

Embodiment 13

The Li of 1.10 liters of 1.0mol/l ₂SO ₄The Al of solution and 2.00 liters of 1.0mol/l ₂(SO ₄) ₃The mixed solution of solution joins in the stainless steel vessel, stirs the NaOH solution that injects 4.00 liters of 3.0mol/l down, keeps 30min.Then this reaction paste is moved into autoclave, 170 ℃ of hydrothermal treatment consists 6h.After cooling off then and filtering, wash, dehydrate is joined in the stainless steel vessel that adds ion exchanged water, 90 ℃ heat after, stir down and add with SiO ₂The sodium silicate solution (No. 3 water glass) of 1.960 liters of 1.0mol/l that convert also stirs 3h.Continue to measure 23.3g stearyl phosphoric acid ester (purity 99%), after suspending in the diluted sodium hydroxide solution of heating, join in the slurry, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Li _0.97Al ₂(OH) ₆(polymer Si _2.49O _5.98) _0.393(SO ₄) _0.075(CO ₃) _0.0170.50H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.19, and Si is to Al ₂O ₃Mol ratio be 0.98.Also have, BET is 19m ²/ g, average aggregate particle size is 1.00 μ m, the surface treatment adsorptive capacity is 4.5 weight %.

Embodiment 14

The Li of 1.10 liters of 1.0mol/l ₂SO ₄The MgCl of solution and 0.04 liter of 1.0mol/l ₂The Al of solution and 2.00 liters of 1.0mol/l ₂(SO ₄) ₃The mixed solution of solution joins in the stainless steel vessel, stirs the NaOH solution that adds 4.000 liters of 3.0mol/l down, keeps 30min.Then this reaction paste is moved into autoclave, 170 ℃ of hydrothermal treatment consists 6h.After cooling off then and filtering, wash, dehydrate is joined in the stainless steel vessel that adds ion exchanged water, 90 ℃ heat after, stir the KH that adds 2.00 liters of 1.0mol/l down ₂PO ₄Solution also stirs 3h.Continue to measure 29.6g sodium stearate (purity 86%), after dissolving in the ion exchanged water of heating, join in the slurry, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Li _0.95Mg _0.02Al ₂(OH) ₆(polymer P _2.21O _6.53) _0.444(SO ₄) _0.035(CO ₃) _0.0170.60H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.11, and P is to Al ₂O ₃Mol ratio be 0.98.Also have, BET is 18m ²/ g, average aggregate particle size is 0.77 μ m, the surface treatment adsorptive capacity is 4.4 weight %.

Comparative example 1

With DHT-4A (consonance chemical industry system).

Analytical results is Mg _0.683Al _0.317(OH) ₂(CO ₃) _0.1580.56H ₂O.BET is 15m ²/ g, average aggregate particle size is 0.65 μ m, the surface treatment adsorptive capacity is 2.9 weight %.

Comparative example 2

All operations similarly to Example 1 till hydrothermal treatment consists.Filter after the cooling, wash, then dehydrate is put in the stainless steel vessel that is added with ion exchanged water, stir adding down with SiO ₂The sodium silicate solution of the 0.667 liter of 1.0mol/l that converts is at 90 ℃ of stirring 2h that heat.Measure 18.2g sodium stearate (purity 86%) under continuing to stir, after dissolving in the ion exchanged water of heating, join in the slurry, carry out surface treatment at 90 ℃.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.

Analytical results is Mg _0.692Al _0.308(OH) ₂(HSi _1.00O _3.00) _0.154(SO ₄) _0.054(CO ₃) _0.0230.62H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.50, and Si is to Al ₂O ₃Mol ratio be 1.00.Also have, BET is 22m ²/ g, average aggregate particle size is 0.70 μ m, the surface treatment adsorptive capacity is 4.0 weight %.

Comparative example 3

Open flat 8-217912 (=EP 708,056) [embodiment 2] synthesizes according to the spy.

The Mg (NO of 3 liters of 1.5mol/l ₃) ₂Al (the NO of solution and 0.667 liter of 2.0mol/l ₃) ₃The mixed solution of solution joins in the autoclave, stirs the NaOH solution that injects 2.889 liters of 3.0mol/l down, keeps 30min, 170 ℃ of hydrothermal treatment consists 12h.After being cooled to about 70 ℃ then, will be under stirring with SiO ₂The sodium silicate solution (No. 3 water glass) of 2.667 liters of 1.0mol/l that convert adds in the autoclave, stirs 30min.Then measure 20.4g stearyl phosphoric acid ester (purity 99%), after suspending in the diluted sodium hydroxide solution of heating, join in the autoclave, carry out surface treatment at 70 ℃.Filter at last, with decarbonation washing, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer Si _4.00O _9.00) _0.1540.62H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.00, and Si is to Al ₂O ₃Mol ratio be 4.00.Also have, BET is 21m ²/ g, average aggregate particle size is 0.84 μ m, the surface treatment adsorptive capacity is 4.0 weight %.

Comparative example 4

The sample that obtains equally with comparative example 3 is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Mg _0.692Al _0.308(OH) ₂(polymer Si _4.00O _9.00) _0.1540.04H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.00, and Si is to Al ₂O ₃Mol ratio be 4.00.Also have, BET is 23m ²/ g, average aggregate particle size is 0.80 μ m, the surface treatment adsorptive capacity is 4.4 weight %.

Comparative example 5

The Al of 2 liters of 2.0mol/l (OH) ₃Slurry joins in the stainless steel vessel, stirs to add 88.6g Li down ₂CO ₃Powder stirs 30min.This reaction paste is moved into autoclave, at 140 ℃ of hydrothermal treatment consists 4h.After the cooling, reaction paste is moved in the stainless steel vessel, 80 ℃ heat after, measure 16.3g sodium stearate (purity 86%), join in 80 ℃ of ion exchanged waters of heating after the dissolving, be injected into and carry out surface treatment in the slurry.Filter at last, wash, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.

Analytical results is Li _1.00Al ₂(OH) ₆(CO ₃) _0.503.0H ₂O.BET is 15m ²/ g, average aggregate particle size is 0.90 μ m, the surface treatment adsorptive capacity is 2.9 weight %.

Comparative example 6

Synthesize [embodiment 4] according to the flat again 09-800828 of spy (=USP 5,767,179 and EP778,241).

The Al of 2 liters of 2.0mol/l (OH) ₃Slurry joins in the stainless steel vessel, stirs to add 88.6g Li down ₂CO ₃Powder stirs 30min.This reaction paste is moved into autoclave, at 140 ℃ of hydrothermal treatment consists 4h.After being cooled to room temperature, stir the HNO that in autoclave, slowly adds 5.244 liters of 0.5N down ₃Solution stirs 1h.The sodium silicate solution (No. 3 water glass) that then under agitation adds 2.010 liters 1.0mol/l stirs 1h.Thereafter 70 ℃ heat after, measure 15.7g stearyl phosphoric acid ester (purity 99%), join in 70 ℃ of diluted sodium hydroxide solutions of heating suspend after, be injected into and carry out surface treatment in the autoclave.Filter at last, with decarbonation washing, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Li _1.00Al ₂(OH) ₆(polymer Si _2.00O _5.00) _0.5000.30H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.00, and Si is to Al ₂O ₃Mol ratio be 1.00.Also have, BET is 15m ²/ g, average aggregate particle size is 0.90 μ m, the surface treatment adsorptive capacity is 3.3 weight %.

Comparative example 7

Synthesize [embodiment 1] according to the flat again 09-800828 of spy (=USP 5,767,179 and EP 778,241).

The Al of 2 liters of 2.0mol/l (OH) ₃Slurry joins in the stainless steel vessel, stirs to add 88.6g Li down ₂CO ₃The MgCl of the 1.0mol/l of powder and 0.040 liter ₂Solution stirs 30min.This reaction paste is moved into autoclave, at 140 ℃ of hydrothermal treatment consists 4h.After being cooled to room temperature, stir the HNO that in autoclave, slowly adds 5.404 liters of 0.5N down ₃Solution stirs 1h.The sodium silicate solution (No. 3 water glass) that then under agitation adds 2.090 liters 1.0mol/l stirs 1h.Thereafter 70 ℃ heat after, measure 16.3g stearyl phosphoric acid ester (purity 99%), join in 70 ℃ of diluted sodium hydroxide solutions of heating suspend after, be injected into and carry out surface treatment in the autoclave.Filter at last, with decarbonation washing, 95 ℃ of dryings 1 round the clock after, the sample that obtains pulverizing.This sample is carried out removing of middle water under 200 ℃ of thermal treatment 3h conditions.

Analytical results is Li _0.98Mg _0.02Al ₂(OH) ₆(polymer Si _2.00O _5.00) _0.510.25H ₂O.The ratio that the B negatively charged ion accounts for total valence mumber (X) is 0.00, and Si is to Al ₂O ₃Mol ratio be 1.02.Also have, BET is 16m ²/ g, average aggregate particle size is 0.88 μ m, the surface treatment adsorptive capacity is 3.2 weight %.

＜effect in agricultural film 〉

, mix in 100 ℃ open type roller by cooperation shown below with ethylene-vinyl acetate copolymer (EVA), make the EVA-resin combination, the electric heating press shaping of following with 180 ℃ obtains the thick film of 100 μ m.Dispersiveness (generation of spending in vain) in this film of visual assessment is measured total light penetration, mist degree (turbidity) value with turbidometer, also measures the infrared ray absorption ability, calculates to be incubated exponential.

The prescription of EVA-resin combination

Ethylene-vinyl acetate copolymer (3758,

Vinyl acetate content 15%, Uni-Charm Co., Ltd.'s system) 87.4 weight %

Hindered amine light stabilizer (チマソ-Block 770,

チバガイギ-corporate system) 0.2 weight %

UV light absorber (チヌ-PVC Application 320,

チバガイギ-corporate system) 0.1 weight %

Oxidation inhibitor (イ Le ガノ _StarNetwork ス 1076,

チバガイギ-corporate system) 0.1 weight %

Anti-turbid dose of single Zerol 1.5 weight %

Two Stearic diglycerides, 0.5 weight %

Lubricant stearylamide 0.1 weight %

Antifogging agent (DS-403, ダイキ Application industrial system) 0.1 weight %

Infrared absorbent (embodiment or comparative example) 10 weight %

Embodiment 15

In the EVA-resin combination, be infrared absorbent with embodiment 1.

Embodiment 16

In the EVA-resin combination, be infrared absorbent with embodiment 2.

Embodiment 17

In the EVA-resin combination, be infrared absorbent with embodiment 3.

Embodiment 18

In the EVA-resin combination, be infrared absorbent with embodiment 4.

Embodiment 19

In the EVA-resin combination, be infrared absorbent with embodiment 5.

Embodiment 20

In the EVA-resin combination, be infrared absorbent with embodiment 6.

Embodiment 21

In the EVA-resin combination, be infrared absorbent with embodiment 7.

Embodiment 22

In the EVA-resin combination, be infrared absorbent with embodiment 8.

Embodiment 23

In the EVA-resin combination, be infrared absorbent with embodiment 9.

Embodiment 24

In the EVA-resin combination, be infrared absorbent with embodiment 10.

Embodiment 25

In the EVA-resin combination, be infrared absorbent with embodiment 11.

Embodiment 26

In the EVA-resin combination, be infrared absorbent with embodiment 12.

Embodiment 27

In the EVA-resin combination, be infrared absorbent with embodiment 13.

Embodiment 28

In the EVA-resin combination, be infrared absorbent with embodiment 14.

Comparative example 8

In the EVA-resin combination, be infrared absorbent with comparative example 1.

Comparative example 9

In the EVA-resin combination, be infrared absorbent with comparative example 2.

Comparative example 10

In the EVA-resin combination, be infrared absorbent with comparative example 3.

Comparative example 11

In the EVA-resin combination, be infrared absorbent with comparative example 4.

Comparative example 12

In the EVA-resin combination, be infrared absorbent with comparative example 5.

Comparative example 13

In the EVA-resin combination, be infrared absorbent with comparative example 6.

Comparative example 14

In the EVA-resin combination, be infrared absorbent with comparative example 7.

Comparative example 15

In the EVA-resin combination, do not cooperate infrared absorbent.

Table 1 shows the evaluation result of embodiment 15～28 and comparative example 8～15.

Table 1

	The insulation index	Total light penetration	Mist degree	Dispersed (range estimation)
	The insulation index	Total light penetration	Mist degree	Dispersed (range estimation)	Embodiment 15	85	89	4	Well
Embodiment 16	86	90	4	Well	Embodiment 15	85	89	4	Well
Embodiment 16	86	90	4	Well	Embodiment 17	86	90	5	Well
Embodiment 18	84	90	4	Well	Embodiment 17	86	90	5	Well
Embodiment 18	84	90	4	Well	Embodiment 19	84	90	5	Well
Embodiment 20	86	90	4	Well	Embodiment 19	84	90	5	Well
Embodiment 20	86	90	4	Well	Embodiment 21	86	90	5	Well
Embodiment 22	86	90	5	Well	Embodiment 21	86	90	5	Well
Embodiment 22	86	90	5	Well	Embodiment 23	85	90	4	Well
Embodiment 24	84	90	5	Well	Embodiment 23	85	90	4	Well
Embodiment 24	84	90	5	Well	Embodiment 25	84	90	4	Well
Embodiment 26	84	90	5	Well	Embodiment 25	84	90	4	Well
Embodiment 26	84	90	5	Well	Embodiment 27	85	90	5	Well
Embodiment 28	85	90	5	Well	Embodiment 27	85	90	5	Well
Embodiment 28	85	90	5	Well	Comparative example 8	80	88	10	Well
Comparative example 9	82	88	10	Well	Comparative example 8	80	88	10	Well
Comparative example 9	82	88	10	Well	Comparative example 10	83	89	10	Well
Comparative example 11	83	90	14	Well	Comparative example 10	83	89	10	Well
Comparative example 11	83	90	14	Well	Comparative example 12	80	89	15	Well
Comparative example 13	84	89	14	Well	Comparative example 12	80	89	15	Well
Comparative example 13	84	89	14	Well	Comparative example 14	84	89	14	Well
Comparative example 15	55	92	2	-	Comparative example 14	84	89	14	Well

Under 180 ℃, make metallocene PE resin combination by following prescription with metallocene PE (PE) with the single shaft muller, then under 160 ℃ with the T shape die head forcing machine thick film of 100 μ m that is shaped.Use this film, carry out the mensuration same with EVA.

Metallocene PE-resin combination

Metallocene PE (KF-270,

Japan Port リケ system corporate system) 87.3 weight %

Hindered amine light stabilizer (TINUVIN622,

チバガイギ-corporate system) 0.2 weight %

UV light absorber (チヌ-PVC Application 320,

チバガイギ-corporate system) 0.1 weight %

Oxidation inhibitor (イ Le ガノ _StarNetwork ス 1010, チバガイギ-corporate system) 0.1 weight %

(イ Le ガ Off _オス 168, チバガイギ-corporate system) 0.1 weight %

Anti-turbid dose of single Zerol 1.5 weight %

Two Stearic diglycerides, 0.5 weight %

Lubricant stearylamide 0.1 weight %

Antifogging agent (KF-345, chemical company of SHIN-ETSU HANTOTAI system) 0.1 weight %

Infrared absorbent (embodiment or comparative example) 10 weight %

Embodiment 29

Use embodiment 2 as infrared absorbent in the metallocene PE-resin combination.

Embodiment 30

Use embodiment 3 as infrared absorbent in the metallocene PE-resin combination.

Embodiment 31

Use embodiment 4 as infrared absorbent in the metallocene PE-resin combination.

Embodiment 32

Use embodiment 5 as infrared absorbent in the metallocene PE-resin combination.

Embodiment 33

Use embodiment 6 as infrared absorbent in the metallocene PE-resin combination.

Embodiment 34

Use embodiment 9 as infrared absorbent in the metallocene PE-resin combination.

Embodiment 35

Use embodiment 13 as infrared absorbent in the metallocene PE-resin combination.

Comparative example 16

Use comparative example 1 as infrared absorbent in the metallocene PE-resin combination.

Comparative example 17

Use comparative example 2 as infrared absorbent in the metallocene PE-resin combination.

Comparative example 18

Use comparative example 4 as infrared absorbent in the metallocene PE-resin combination.

Comparative example 19

Use comparative example 5 as infrared absorbent in the metallocene PE-resin combination.

Comparative example 20

Use comparative example 6 as infrared absorbent in the metallocene PE-resin combination.

Comparative example 21

Do not cooperate infrared absorbent in the metallocene PE-resin combination.

Comparative example 22

Only with metallocene PE-resin (additive-free).

Table 2 shows the evaluation result of embodiment 29～35 and comparative example 16～22.

Table 2

	The insulation index	Total light penetration	Mist degree	Dispersed (range estimation)
	The insulation index	Total light penetration	Mist degree	Dispersed (range estimation)	Embodiment 29	77	90	4	Well
Embodiment 30	77	90	5	Well	Embodiment 29	77	90	4	Well
Embodiment 30	77	90	5	Well	Embodiment 31	76	90	4	Well
Embodiment 32	75	90	4	Well	Embodiment 31	76	90	4	Well
Embodiment 32	75	90	4	Well	Embodiment 33	77	89	5	Well
Embodiment 34	76	90	4	Well	Embodiment 33	77	89	5	Well
Embodiment 34	76	90	4	Well	Embodiment 35	77	89	4	Well
Comparative example 16	67	89	8	Well	Embodiment 35	77	89	4	Well
Comparative example 16	67	89	8	Well	Comparative example 17	73	89	8	Well
Comparative example 18	77	89	10	Well	Comparative example 17	73	89	8	Well
Comparative example 18	77	89	10	Well	Comparative example 19	72	88	13	Well
Comparative example 20	77	88	11	Well	Comparative example 19	72	88	13	Well
Comparative example 20	77	88	11	Well	Comparative example 21	28	91	3	-
Comparative example 22	28	92	1	-	Comparative example 21	28	91	3	-

Above-mentioned film is carried out accelerated weathering test with daylight weatherometer (Shimadzu Seisakusho Ltd.'s system).Result by the visual observations of the film behind the 750h shows that the film of the independent metallocene PE of comparative example 22 is serious aging (sclerosis).Also have, just do not cooperate the film surface ag(e)ing and leaking gas only of the comparative example 21 of infrared absorbent.But, also cooperated the film of infrared absorbent, all the surface ag(e)ing degree than comparative example 22 is slow for which, and almost can't see gas leakage.

Mixing by 180 ℃ open type roller with polyvinyl chloride (PVC, molecular-weight average 1000, chemical company of SHIN-ETSU HANTOTAI system) by following prescription, make the PVC-resin combination, obtain the thick film of 100 μ m with the shaping of 180 ℃ electric heating press then.Carry out the mensuration same with this film with EVA.

The PVC base resin composition

Polyvinyl chloride (molecular-weight average 1000, chemical company of SHIN-ETSU HANTOTAI system) 57.89 weight %

Plasticizer DOP (dioctyl phthalate (DOP)) 30 weight %

Tritolyl phosphate 3 weight %

Bisphenol A type epoxy resin 1.5 weight %

Hindered amine light stabilizer (チマソ-Block 119,

チ Ha カイギ-corporate system) 0.1 weight %

UV light absorber (チヌ-PVC Application 329,

チバガイギ-corporate system) 0.05 weight %

Oxidation inhibitor (イ Le ガノ _StarNetwork ス 1076,

チバガイギ-corporate system) 0.05 weight %

Anti-turbid dose of sorbitan monopalmitate 1.0 weight %

Lubricant methylene radical distearyl acid amides 0.3 weight %

Thermo-stabilizer Ba-Zn class stablizer 1.0 weight %

Phenyl phenacyl ketone 0.01 weight %

Infrared absorbent (embodiment or comparative example) 5 weight %

Embodiment 36

Using embodiment 3 in the PVC-resin combination is infrared absorbent.

Embodiment 37

Using embodiment 7 in the PVC-resin combination is infrared absorbent.

Embodiment 38

Using embodiment 10 in the PVC-resin combination is infrared absorbent.

Embodiment 39

Using embodiment 14 in the PVC-resin combination is infrared absorbent.

Comparative example 23

Using comparative example 1 in the PVC-resin combination is infrared absorbent.

Comparative example 24

Using comparative example 4 in the PVC-resin combination is infrared absorbent.

Comparative example 25

Using comparative example 7 in the PVC-resin combination is infrared absorbent.

Comparative example 26

Do not cooperate infrared absorbent in the PVC-resin combination.

Table 3 shows the evaluation result of embodiment 36～39 and comparative example 23～26.

Table 3

	The insulation index	Total light penetration	Mist degree	Dispersed (range estimation)
	The insulation index	Total light penetration	Mist degree	Dispersed (range estimation)	Embodiment 36	89	91	5	Well
Embodiment 37	89	91	4	Well	Embodiment 36	89	91	5	Well
Embodiment 37	89	91	4	Well	Embodiment 38	89	91	4	Well
Embodiment 39	89	91	4	Well	Embodiment 38	89	91	4	Well
Embodiment 39	89	91	4	Well	Comparative example 23	85	91	5	Well
Comparative example 24	88	90	6	Well	Comparative example 23	85	91	5	Well
Comparative example 24	88	90	6	Well	Comparative example 25	88	91	6	Well
Comparative example 26	78	91	3	-	Comparative example 25	88	91	6	Well

Also have, Fig. 1 shows the infrared ray absorption spectrum of 100 μ m thick film of the hydrotalcite-based compound of the present invention (powder) of the embodiment 2 that contains 10 weight % in metallocene PE (PE).

Fig. 2 shows the infrared ray absorption spectrum of 100 μ m thick film of the hydrotalcite-based compound of the present invention (powder) of the embodiment 3 that contains 10 weight % in metallocene PE.

Fig. 3 shows the infrared ray absorption spectrum of 100 μ m thick film of the hydrotalcite-based compound of the present invention (powder) of the embodiment 9 that contains 10 weight % in metallocene PE.

Fig. 4 shows the infrared ray absorption spectrum of 100 μ m thick film of the hydrotalcite-based compound (powder) of the comparative example 1 that contains 10 weight % in metallocene PE.

Fig. 5 shows the just infrared ray absorption spectrum of the 100 μ m thick film of metallocene PE.

The commercial Application possibility

Of the present inventionly maintain with at least a anion and its part in silicon class, the Phosphorus and boron class oxyacid radical ion and/or all be at least a anion in silicon class, the Phosphorus and boron class poly oxyacid radical ion and the hydrotalcite-based compound of at least a anion in the anion in addition thereof at interlayer, has the infrared ray absorbing ability than always hydrotalcite-based compound excellence, simultaneously, in the time of in being contained in the thermoplastic resin of using as agricultural film, it can give the light trafficability characteristic of film with excellence. Particularly, the following and BET specific area 30m of average aggregate particle size 5 μ m²The product that/g is following and surface treatment hydrotalcite-based compound, to the favorable dispersibility of agricultural film with thermoplastic resin. In the preparation of hydrotalcite-based compound of the present invention, can provide cheap product more cheap so prepare sulfate ion type product when synthetic by reaction.

When being included in the agricultural film as infrared absorbent, can provide the agricultural film that has excellent heat insulating ability and excellent light trafficability characteristic concurrently hydrotalcite-based compound of the present invention. Also have, with various additives and usefulness, just can provide have excellent weatherability, the agricultural film of the continuation excellence of resin aging that anti-turbid property, antifog property, dust tightness, anti-drop property, toughness, resistance to pesticide, acid rain resistant, heat resistance, fading property, antibiotic property, mildew resistance, stretching and preventing causes because of various additives and these characteristics.

Claims

1. with the hydrotalcite-based compound of following formula (1) or (2) expression, it is characterized in that, maintain as the negatively charged ion of interlayer and be at least a negatively charged ion in silicon class, the Phosphorus and boron class oxygen acid radical ion and its part and/or all be at least a negatively charged ion and the negatively charged ion beyond it in silicon class, the Phosphorus and boron class poly oxygen acid radical ion;

＜magnesium-aluminum hydrotalcite compounds 〉

[(Mg _y1M ²⁺ _y2) _1-xAl _x(OH) ₂] ^x+[(A) _z1(B) _z2·bH ₂O] ^x- …(1)

(basic layer) (interlayer)

M ²⁺At least a divalent metal ion in expression zinc, calcium and the nickel, A represents at least a negatively charged ion in silicon class, the Phosphorus and boron class oxygen acid radical ion and represents its part and/or all be at least a negatively charged ion in silicon class, the Phosphorus and boron class poly oxygen acid radical ion

B represents it is at least a negatively charged ion in the negatively charged ion beyond the A,

X, y1, y2, z1, z2 and b satisfy following condition separately:

X is 0＜X≤0.5;

Y1 and y2 are y1+y2=1,0＜y1≤1,0≤y2＜1;

Z1 and z2 are 0＜z1,0＜z2;

B is 0≤b＜2;

＜lithium-aluminum hydrotalcite compounds 〉

[(Li _y1G ²⁺ _y2)Al ₂(OH) ₆] ^x+[(A) _z1(B) _z2·b _H2O] ^x- …(2)

(basic layer) (interlayer)

G ²⁺At least a divalent metal ion in expression magnesium, zinc, calcium and the nickel, A is expressed as at least a negatively charged ion in silicon class, the Phosphorus and boron class oxygen acid radical ion and represents its part and/or all be at least a negatively charged ion in silicon class, the Phosphorus and boron class poly oxygen acid radical ion

Y1, y2, X, z1, z2 and b satisfy following condition separately:

Y1 and y2 are 0＜y1≤1,0≤y2＜1,0.5≤(y1+y2)≤1;

X is X=y1+2y2;

Z1 and z2 are 0＜z1,0＜z2; B is 0≤b＜5.

2. the described hydrotalcite-based compound of claim 1 is characterized in that, the represented negatively charged ion of the B in formula (1) or (2) is at least a negatively charged ion in sulfate ion, carbanion, chlorion and the nitrate ion.

3. claim 1 or 2 described hydrotalcite-based compounds is characterized in that, the represented negatively charged ion of the B in formula (1) or (2) is at least a negatively charged ion in sulfate ion and the carbanion.

4. any one described hydrotalcite-based compound of claim 1～3 is characterized in that, is the scope of following formula in formula (1) or (2): in formula (1) and (2),

5. any one described hydrotalcite-based compound of claim 1～4, it is characterized in that A is represented in the formula (1) be anionic silicon class and/or Phosphorus oxygen acid radical ion as the mole number (Q) of Si and/or P is the scope of following formula: 0＜Q/ is (as Al ₂O ₃Mole number)＜2.

6. any one described hydrotalcite-based compound of claim 1～4 is characterized in that, A is represented in the formula (2) be anionic silicon class oxygen acid radical ion as the mole number (R) of Si is the scope of following formula: 0＜R/ is (as Al ₂O ₃Mole number)＜1.

7. any one described hydrotalcite-based compound of claim 1～6, it is characterized in that it is to have crossed surface-treated with at least a surface treatment agent in fatty acid ester of higher fatty acid, aniorfic surfactant, phosphoric acid ester, nonionic surface active agent, silane, titanic acid ester and aluminium class coupler and polyvalent alcohol etc.

8. any one described hydrotalcite-based compound of claim 1～7 is characterized in that, its average aggregate particle size below 5 μ m and the BET specific surface area at 30m ²Below/the g.

9. an infrared absorbent is characterized in that, it is as effective constituent with any one described hydrotalcite-based compound of claim 1～8.

10. an infrared absorbent is characterized in that, it is to be effective constituent with middle water by any one described hydrotalcite-based compound of the claim 1～8 of partly or entirely removing.

11. an agricultural film is characterized in that, it is constituted by the claim 9 of 1～30 weight % and/or at least a film configuration in the 10 described infrared absorbents by containing with respect to thermoplastic resin.

12. the preparation method of any one described hydrotalcite-based compound of claim 1～7, it is characterized in that, at first, preparation is the hydrotalcite-based compound of main interlayer anion with sulfate ion when reaction is synthetic, then at 60 ℃～100 ℃ with at least a negatively charged ion in silicon class, the Phosphorus and boron class oxygen acid radical ion and its part and/or all be that at least a negatively charged ion in silicon class, the Phosphorus and boron class poly oxygen acid radical ion carries out ion-exchange.